Acrylonitrile-capped polyether-siloxane

ABSTRACT

Acrylonitrile-capped polyoxyalkylene compounds; siloxane polymers modified with the corresponding radicals of said compounds; solvent compositions containing said siloxane polymers; a process for producing polyurethane foam using said siloxane polymers as the foam stabilizer; and the foam produced from said process.

BACKGROUND OF THE INVENTION

The present invention relates to a particular novel class ofacrylonitrile-capped polyoxyalkylene compounds and toacrylonitrile-capped polyoxyalkylene-polysiloxane polymers, as well asto the use of said polymers in the formation of cellular urethaneproducts, particularly flexible polyester urethane foam containing aflame-retardant.

It is well known that the urethane linkages of cellular urethanes areformed by the exothermic reaction of a polyfunctional isocyanate and apolyfunctional active hydrogen-containing compound in the presence of acatalyst, and that the cellular structure is provided by gas evolutionand expansion during the urethane-forming reaction. Illustrative ofsuitable active hydrogen-containing compounds are polyester polyols andpolyester polyols. In accordance with the "one-shot" process which isthe most widely used industial technique, direct reaction is effectedbetween all of the raw materials which include the polyisocyanate, theactive hydrogen-containing compound, the catalyst system, blowing agentand surfactant. A major function of the surfactant is to stabilize theurethane foam, that is, prevent collapse of the foam until the foamedproduct has developed sufficient gel strength to become self-supporting.Among the various types of silicon-containing compositions reported inthe literature as effective stabilizers of urethane foam derived from apolyester polyol and a polyether polyol are e.g. those described in U.S.Pat. No. 3,594,334 and U.S. Pat. No. 27,541, respectively. Other patentsrelating to the manufacture of flexible polyester urethane foam includeU.S. Pat. Nos. 3,563,924; 3,793,360; 3,796,676 and 3,833,512.

In recent years considerable effect has been expended and continues, toreduce the recognized objectionable characteristics of urethane polymersin their ability to ignite readily and burn with an open flame. Oneapproach to this problem is to include flame-retarding agent such asvarious phosphrus and/or halogen-containing compounds as a component ofthe foam-producing reaction mixture, and in this respect, to developimproved and more efficient flame-retarding agents. As associatedproblem is to provide surfactants which not only function to stabilizefoam containing a flame-retarded but which also allow for the formationof such foam which burns at a reduced rate relative to surfactantsdesigned for stabilization of non-flame-retarded foam. For example,certain siloxane surfactants which are excellent stabilizers ofnon-flame-retarded foam and which are also capable of stabilizing foamcontaining a flame-retardant appear to have an adverse effect on theefficiency of the flame retarding agent as seen from the flamabilityproperties of some resulting flexible polyester urethane foam products.

It is desirable, therefore, and is an object of this invention toprovide a new class of acrylonitrile-capped polyoxyalkylene compounds aswell as a new class of acrylonitrile-capped polyoxyalkylene-polysiloxanepolymers which polymers, in addition to the ability to stablize nonflame-retarded cellular urethanes, offer particular utility asstabilizers of flexible polyester urethane foam having a flame-retardantincorporated therein.

Various other objects and advantages of this invention will becomeapparent to those skilled in the art from the accompanying descriptionand the disclosure.

SUMMARY OF THE INVENTION

In accordance with one aspect of the present inventionacrylonitrile-capped polyoxyalkylene compounds are provided which can beused to produce the acrylonitrile-capped polyoxyalkylene-polysiloxanepolymers employed in this invention.

Illustrative of the novel class of acrylonitrile-capped polyoxyalkylenecompounds of this invention are those having the average formula

    R'(X).sub.q (OC.sub.3 H.sub.6).sub.n (OC.sub.2 H.sub.4).sub.m OCH.sub.2 CH.sub.2 CN

wherein X is a bridging group selected from the class consiting of--CO--and --NHCO--; wherein R' represents a monovalent olefinic alkyleneradical containing from 2 to 6 carbon atoms and usually not more than 4,allyl being preferred; wherein q has a value of 0 or 1; preferably 0;wherein m has a value of from 4 to 30, preferably 4 to 15; wherein n hasthe value of from 0 to 10, preferably 0, and wherein the sum of m + nhas a value of from 4 to 40, preferably 4 to 15.

Another aspect of this invention provides acrylonitrile-cappedpolyoxyalkylene-polysiloxane polymers, said polymers containing at leastone silicon-bonded acrylonitrile-capped polyoxyalkylene radical (Q)wherein Q has the average formula

    --R"(X).sub.q (OC.sub.3 H.sub.6).sub.n (OC.sub.2 H.sub.4).sub.m OCH.sub.2 CH.sub.2 CN

wherein X, q, n and m are the same as defined above and R" represents analkylene radical, free from unsaturation, and containing from 2 to 6carbon atoms, usually not more than 4. The preferred alkylene radical R"being propylene. Of course, it is obvious that said alkylene radical R"is derived from and corresponds to the particular R' group of the abovedefined acrylonitrile-capped polyoxyalkylene compounds used in theproduction of the novel siloxane polymers of this invention and it is ofcourse also understod that said alkylene radical R" is directly bondedto a silicon atom which constitutes one of the siloxy units of saidacrylonitrile-capped polyoxyalkylene-polysiloxane polymers of thisinvention. It is of course also understood that the other siloxy unitsas well as other radicals attached thereto that make up the siloxanepolymers of this invention are well known in the art and obviously cancorrespond to those siloxy units and radicals heretofore contained inconventional siloxane surfactants that may be employed as stabilizers inthe production of urethane foam and therefore are not critical to thegeneric definition of the siloxane polymers of this invention.

Illustrative of a preferred class of siloxane polymers of this inventionare acrylonitrile-capped polyoxyalkylene polymers consisting essentiallyof chemically combined (1) monofunctional siloxy units (M^(o)) and (2)an average of from about 0.5 to about 70 moles of difunctional siloxyunits (D^(o)) for every 2 moles of M^(o), with the proviso that anaverage of at least about 0.5 up to about 30 moles ofacrylonitrile-capped polyoxyalkylene groups (Q) are present in saidacrylonitrile-capped polyoxyalkylene-polysiloxane polymers for every 2moles of M^(o), wherein Q is the same as defined above.

In the monofunctional siloxy units encompassed by M^(o) of said polymersthe respective silicon atoms are bonded to two monovalent hydrocarbonradicals (R), preferably alkyl group, the third silicon-bonded groupbeing the aforesaid acrylonitrile-capped polyoxyalkylene group (Q), amonovalent hydrocarbon group (R) or E^(o) a radical selected from theclass consisting of a cyano-containing group (E) of the formula--(O)_(r) R² CN wherein r is 0 or 1, preferably 0 and R² is an alkyleneradical having from 2 to 12 carbon atoms preferably 2 to 4, acyano-containing group (E¹) of the formula --(O)_(r) R² OR² CN wherein rand R² are the same as defined above; a sulfolanyloxyalkyl-containinggroup (E²) of the formula ##STR1## wherein R³ is an alkylene radicalhaving from 2 to 8 carbon atoms and R⁴, R⁵, R⁶ and R⁷ shown bonded tothe carbon atoms in the two to five positions of the ring, respectively,are independently hydrogen and alkyl having from 1 to 4 carbon atoms,and a morpholino-containing group (E³) of the formula ##STR2## wherein tis 0 or has an average value from about 1 to about 4; s 0 or 1 provideds is 1 when t has a value of more than 1; R⁸ is an alkylene radicalhaving from 2 to 4carbon atoms, R⁹ is an alkylene radical having from 2to 6 carbon atoms and R⁴, R⁵, R⁶ and R⁷ are the same as defined above.Thus, included with the scope of M^(o) are monofunctional siloxy unitshaving the following unit formulae which for brevity are alsoindividually referred to herein as the M, M¹, M², M³, M⁴, and M⁵ unitsas shown:

    M=R.sub.3 SiO1/2

    m.sup.1 =(q)r.sub.2 siO1/2

    m.sup.2 =(e)r.sub.2.sup.2 siO1/2

    m.sup.3 =(e.sup.1)r.sub.2 siO1/2

    m.sup.4 =(e.sup.2)r.sub.2 siO1/2

    m.sup.5 =(e.sup.3)r.sub.2 siO1/2

of course in any given polymer composition the M^(o) units may be thesame as or different from one another. In the difunctional unitsemcompassed by D^(o), at least one of the two groups bonded to therespective silicon atoms is a monovalent hydrocarbon radical (R),preferably alkyl, and the second silicon-bonded group is Q, E^(o) or R.Thus, included within the scope of D^(o) are difunctional units havingthe following unit formulae which for brevity, are also individuallyreferred to herein as the D, D¹, D², D³, D⁴ and D⁵ units are shown

    D=R.sub.2 SiO2/2

    d.sup.1 =(q)(r)siO2/2

    d.sup.2 =(e)rsiO2/2

    d.sup.3 =(e.sup.1)rsiO2/2

    d.sup.4 =(e.sup.2)rsiO2/2

    d.sup.5 =(e.sup.3)rsiO2/2

thus, said preferred class of the polymers may contain any combinationor subcombination of the respective siloxy units within the scope ofM^(o) and D^(o) provided the average composition contains from about 0.5to about 70 moles of D^(o) for every 2 mols of M^(o) and from about 0.5to about 30 moles of Q for every 2 moles of M^(o).

Consistent with the above definition and from the standpoint of thenature and relative proportion of monomeric siloxy units, the abovepreferred class of acrylonitrile-capped polyoxyalkylene-polysiloxanepolymers have the following average composition, as expressed on thenormalized basis of a total of two moles of monofunctional units(M^(o)), that is, per average mole of polymer: ##STR3## wherein R, Q andE^(o) are the same as defined above, wherein a, b, and c are 0 or anypositive number having an average value of no more than 2, and theaverage value of the sum a+b+c is 2; wherein d is 0 or any positivenumber having an average value of up to about 20, e is 0 or any positivenumber having an average value of up to about 30, and f is 0 or anypositive number having an average value up to about 20, provided thataverage value of the sum b+e is at least about 0.5 up to about 30.

It is evident, therefore, that the sum b+e corresponds to the totalnumber of Q groups contained in an average mole of polymer and that wheneither b or e is 0, the other must be at least 0.5. It is also evidentthat when any combination of a, b and c are positive numbers thepolymers contain said combination of respective monofunctional units.

Another prepared class of acrylonitrile-cappedpolyoxyalkylene-polysiloxane polymers are those polymers consistingessentially of silicon-containing units A, B and C wherein A is SiO4/2,B is a polyfunctional siloxy unit in which silicon is bonded to at leastone acrylonitrile-capped polyoxylakylene group (Q) as defined above, andC is a monofunctional triorganosiloxy unit, and in which there are fromabout 0.4 about 2 moles of A, and from about 0.2 to about 2 moles of C,per mole of B.

Yet another class of acrylonitrile-capped polyoxyalkylene-polysiloxanepolymers are those polymers consisting essentially of silicon-containingunits, A', B' and C', wherein A' is SiO4/2, B' is a mono-functionalsiloxy unit in which silicon is bonded to at least oneacrylonitrile-capped polyoxyalkylene group (Q) as defined above, and C'is a monofuctional trihydrocarbylsiloxy unit, and which there are fromabout 0.75 to about 2 moles of A', and from about 0.1 to about 1 mole ofC', per mole of B'.

In accordance with another aspect of the present invention, there isprovided a process for producing polyurethane foam which comprisesreacting and foaming a reaction mixture of: (a) an organic polyolreactant comprising a polyether polyol or a polyester polyol containingan average of at least two hydroxyl groups per molecule; (b) apolyisocyanate reactant containing at least two isocyanato groups permolecule; (c) a blowing agent; (d) a catalyst comprising atertiary-amine; and (e) a foam stabilizing component comprising theacrylonitrile-capped polyoxyalkylene-polysiloxane polymers of thepresent invention. In addition to their efficacy as stabilizers ofnon-flame retardant urethane foam, it has been found that certainpolymers described herein possess the further advantageous property ofallowing for the formation of flame-retardant containing flexiblepolyester foam of acceptable overall quality, and reduced combustibilityrelative to unmodified polyalkylsiloxane-polyoxyalkylene copolymers. Inaccordance with this aspect of the present invention, flame-retardantcontaining flexible polyester-based urethane foam products are providedby reacting and foaming respective reaction mixtures which additionallyinclude a flame-retarding agent.

In providing the polyurethane foams of the invention, theacrylonitrile-capped polyoxyalkylene-polysiloxane polymers can beintroduced to the foam producing reaction mixture either as such, as ablend with various organic additives including organic surfactants or incombination with one or more of the polyol reactant, blowing agent,amine catalyst and, when used, the flame-retarding agent.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The acrylonitrile-capped polyoxyalkylene compounds of this inventionwhich are used as reactants to produce the acrylonitrile-cappedpolyoxyalkylene-polysiloxane polymers of this invention can be made bythe cyanoethylation reaction of olefinic-started and hydroxyl andendblocked polyoxyalkylene compounds.

The olefinic and hydroxyl endblocked polyoxyalkylene compounds and/ormethods for their preparation as well known in the art. For instance byreacting an alkenol, R'OH, an olefinic carboxylic acid R'COOH or anolefinic R'NHCOOH wherein R' is the same as defined above with ethyleneoxide or a mixture of ethylene oxide and 1,2-propylene oxide in thepresence of a base catalyst, e.g. KOH the corresponding olefinic andhydroxyl endblocked polyoxyalkylene compound having the formula

    R'(X).sub.q (OC.sub.3 H.sub.6).sub.n (OC.sub.2 H.sub.4).sub.m OH

can be produced wherein R', X, q, n and m are the same as defined above.Illustrative examples of such hydroxyl starters are H₂ C═CHOH, H₂C═CH--CH₂ OH, H₂ C═C(CH₃)--CH₂ OH, H₂ C═CH--CH₂ COOH, H₂ C═CH--CH₂NHCOOH, and the like. Of course it is understood that when thepolyoxyalkylene compound contains both oxyethylene and oxypropyleneunits that such oxyalkylene units can be randomly distributed throughoutthe chain such as when a mixture of the alkylene oxides is polymerizedor they can be arranged as sub-blocks in any desired fashion such aswhen the respective alkylene oxides are polymerized sequentially.

Conventional cyanoethylation of such olefinic started and hydroxylendblocked polyxoyalkylenes in the presence of a base catalyst thenproduces the corresponding arcylonitrile-capped (i.e. beta-substitutedpropionitrile) polyoxyalkylene compounds of this invention asillustrated by the following equation ##STR4## wherein R', X, q n and mare the same as defined above. As pointed out above preferably R' isallyl, q is 0, n is 0 and m is 4 to 15. Thus, the most preferredacrylonitrile capped polyoxyalkylene compounds are those having theaverage formula

    CH.sub.2 ═CHCH.sub.2 (OC.sub.2 H.sub.4).sub.m OCH.sub.2 CH.sub.2 CN

wherein m is 4 to 15 which compounds are derived from thecyanoethylation of an allyl alcohol started and hydroxy end blockedpolyoxyethylene. High conversions of said acrylonitrile-cappedpolyoxyalkylene compounds are readily achieved by using essentiallystoichiometric amounts of acrylonitrile and (CH₃)₄ NOH or NaOH basecatalysts. The cyanoethylation rate of about 10° C. to about 20° C. isfast and about 90-95 percent complete in less than 2 hours. The use of(CH₃)₄ NOH catalyst is prepared over NaOH mainly because of cappingefficiency and less acrylonitrile homopolymer formation. As indicatedabove, the acrylonitrile capped polyoxy-alkylene compounds of thisinvention are useful as reactants in preparing the acrylonitrile cappedpolyoxyalkylene-polysiloxane polymers of this invention.

The functionality of the respective types of structural unitsencompassed by M^(o), D^(o), A, B, C, and A', B', C', of the siloxanepolymers of this invention denotes the number of oxygen atoms to whichthe silicon atoms (Si) of any particular unit is bonded. Since eachoxygen atom is shared by a silicon atom (Si') of another unit,functionality also denotes the number of linkages by which theparticular unit can be bonded to another portion of the polymer through--Si--O--Si'--bonds. Accordingly, in expressing the individual formulasof the respective units of the polymers of this invention, fractionalsubscripts are used in which the values of the numerator definesfunctionality (i.e., the number of oxygen atoms associated with thesilicon atom of the particular unit), and the denominator, which in eachinstance is 2, denotes that each oxygen atom is shared with anothersilicon atom. Thus, monofunctional units e.g. M^(o), are chainterminating or end-blocking units and the respective oxygen atomsthereof are shared with silicon of one anther unit, e.g. D^(o). On theother hand, D^(o) units are difunctional and thus the respective twooxygen atoms associated with each silicon atom thereof are shared withrespective silicon atoms of other units. Thus, the reoccurringdifunctional units may be distributed in the polymer randomly,alternatively, as sub-blocks of repeating units of the same type, or inany combination of such arrangements. Although the siloxane polymers ofthis invention can be discrete chemical compounds, they are usuallymixtures of discrete siloxane species which differ in molecular weightand in the type, arrangement and relative proportions of units.Therefore, as expressed herein, the parameters employed to denote thesevariables are average values and are based on the relative proportionsof reactants from which the various units are derived. It is to tofurther understood that, consistent with convention in the art to whichthe present invention pertains, as expressed herein, the formulas of thepolymers indicate their overall average emperical composition ratherthan any particular polymer species.

With this understanding the average composition of some of the morepreferred respective types of polymers emcompassed by siloxane polymersof this invention the following formulae wherein the various siloxyunits are shown in chemically combined form: ##STR5## wherein R, Q, E,E¹, E² and E³ are the same as defined above, x has an average value of0.5 to 20; y has an average value of 0.5 to 30 and z has an averagevalue of 0.5 to 20.

Another illustrated class of siloxane polymers of ths invention arethose having the average formula ##STR6## wherein R and Q are the sameas defined above and wherein the mole ratio of the SiO4/2 units to totalpolyfunctional units to total monofunctional units is defined by g:h:iin which the ratio of g:h is from about 0.4:1 to about 2:1, and theratio of i:h is from about 0.2:1 to about 2:1.

Yet another illustrated class of siloxane polymers of this invention arethose having the average formula ##STR7## wherein R and Q are the sameas defined above and wherein the mole ratio of the SiO4/2 units to totalQ substituted siloxy units to total trihydrocarbylisiloxy units isdefined by j:k:p in which the ratio of j:k is from about 0.75:1 to about2:1, and the ratio of p:k is from about 0.1:1 to about 1:1.

The silicone-bonded bonded R groups are monovalent hydrocarbon radicalscontaining from 1 to about 20 carbon atoms and preferably are alkylradicals having from one to ten carbon atoms including linear andbranched alkyls. Illustrative of suitable groups encompassed by R aremethyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl,octyl, decyl and the like. Of the various groups represented by R, thelower alkyls (that is, those having from one to four carbon atoms) aremore preferred of which methyl is especially suitable. It is to beunderstood that the R groups may be the same throughout the polymers orthat may differ as between or within units departing from the scope ofthis invention. For example, when the endblocking monofunctional unitsare M, that is, R₃ SiO1/2--, that may be trimethylsiloxy units and thedifunctional units, R₂ SiO2/2, when present, may be diethylsiloxy and/ormethhylethylsiloxy units. The most preferred M and D siloxy units are(CH₃)₃ SiO1/2 and (CH₃)₂ SiO2/2 respectively.

In the Q substitutents of the siloxane portion of the polymers of thisinvention, that is in the silicon-bonded acrylonitrile-cappedpolyoxyalkylene radical.

    --R"(X).sub.q (OC.sub.3 H.sub.6).sub.n (OC.sub.2 H.sub.4).sub.m OCH.sub.2 CH.sub.2 CN

r", x, q, n and m are as previously defined. As stated R" represents analkylene radical including linear and branched radicals of the series##STR8## wherein w is an integer having from a value of 2 to 8,preferably not more than 4, such as ethylene, 1,2-propylene,1,3-propylene, 1-4-butylene and the like. It is also preferred that qand n are 0 and m has a value of 14 and 15 and most preferably R" is apropylene radical. It is also to be understood that the Q groups may bethe same throughout the polymers or they may differ as between or withinunits without departing from the scope of the invention. Likewise, asstated the oxyethylene and oxypropylene units when both are present maybe randomly distributed or arranged as sub-blocks in any desiredfashion. Illustrative of such preferred M', D' and [RQSiO1/2] siloxyunits are ##STR9## and the like, wherein n and m are the same as definedabove.

In the silicon-bonded, cyano-substituted --(O)_(r) R² CN groups, (groupE above), R² represents an alkylene radical including linear andbranched radicals of the series, --C_(w) H_(2w) --, where w has value offrom 2 to 12, and is usually no more than 6. Illustrative of suitablegroups represented by R² are: ethylene (--CH₂ CH₂ --); 1,3-propylene ortrimethylene (--CH₂ CH₂ CH₂ --); 1,2-propylene [--CH₂ CH(CH₃)--]; andtetramethylene. Most preferably, --R² -- is a lower alkylene grouphaving from 1 to 4 carbon atoms. It is to be understood that the --R² --groups may be the same throughout the polymer or may differ and that thepolymer may contain any combination of cyanoalkyl (--R² CN) andcyanoalkoxy (--OR² CN) substituted siloxy units. Illustrative of suchpreferred M² and D² siloxy units are (gamma-cyanopropyl)di-methylsiloxy;(beta-cyanoethoxy) methylsiloxy; (beta-cyanoethyl) methylsiloxy;(beta-cyanopropyl) methylsiloxy; (gamma-cyanopropyl) methylsiloxy;(gamma-cyanopropyloxy) methylsiloxy; (gamma-cyanopropyl)ethylsiloxy;(gamma-cyanobutyl) methylsiloxy; (delta-cyanobutyl) methylsiloxy, andthe like. The most preferred D² siloxy unit is (gamma-cyanopropyl)methylsiloxy.

In the silicon-bonded, cyanosubstituted --(O)_(r) R² OR² CN groups,(group E¹ above), R² and r are the same as defined above. Among the morepreferred E¹ groups are --(O)_(r) C_(u) H_(2u) OC_(v) H_(2v) --CNwherein r is 0 or 1, u has a value of 3 to 8 and v has a value of 2 to4. It is to be understood that the siloxane polymer may contain anycombination of cyanoalkoxyalkyl (--R² OR² CN) and/or cyanoalkoxyalkoxy(OR² OR² CN) substituted siloxy units. Illustrative of such preferred M³and D³ siloxy units are 3-(2-cyanoethyoxy)propyl methylsiloxy;3-(3-cyanopropoxy)propyl methylsiloxy; 3 -(2-cyanoethoxy) propoxymethylsiloxy; 3-(2-cyanoethoxy)propyl ethylsiloxy;3-(2-cyanoethyl)-2-methylpropyl methylsiloxy; 8-(2-cyanoethyoxy)octylmethylsiloxy; 3-(2-cyano-2-methylethoxy)propyl methylsiloxy;3-(2-cyano-2-ethylethoxy)propyl methylsiloxy; 3-(2-cyanoethoxy)propyldimethylsiloxy; 3-(2-cyanoethoxy)propoxy dimethylsiloxy;3-(2-cyanoethoxy)propyl diethylsiloxy; 3-(2-cyanoethoxy)propylmethylethylsiloxy; and the like. The most preferred D³ siloxy unit is3-(2-cyanoethoxy) propyl methylsiloxy.

In the silicon-bonded, sulfoanyloxyalkyl groups ##STR10## (group E²above) the R⁴ through R⁷ groups are, as previously defined, hydrogen orC₁ to C₄ alkyls. Usually, no more than two are alkyls as in the2,4-dimethylsulfolan-3-yloxyalkyl nucleus. Preferably each of R⁴, R⁵, R⁶and R⁷ is hydrogen. The R³ group is an alkylene radical including linearand branched radicals, of the series, --C_(w) H_(2w) --, wherein w is aninteger having a value from 2 to 8. Illustrative of the linear andbranched saturated alkylene radicals encompassed by --R3-- are ethylene,1,3-propylene or trimethylene; 1,2-propylene; 2-methyl-1,3-propylene1-methyl-1,3-propylene; 1-ethyl-ethylene; 1-4-butylene ortetramethylene; 3-methyl-1, 3-propylene; 3-ethyl-1, 3-propylene;1,5-pentylene or pentamethylene; 4-methyl-1, 4-butylene; 1,6-hexylene orhexamethylene; 1-methyl-3, 3-dimethyl-1, 3-propylene; 1-ethyl-2,2-dimethyl-ethylene; 4,4-dimethyl-1, 4-butylene; 3-propyl-1,3-propylene; 1-ethyl-1; 4-butylene; 1-propyl-1, 3-propylene;1,8-octylene or octamethylene; and the like. Preferably, --R³ -- hasfrom 2 to 6 carbon atoms and most preferably has 3 or 4 carbon atoms.

Illustrative of such preferred M⁴ and D⁴ siloxy units are ##STR11## andthe like. The most preferred D⁴ siloxy unit being one wherein R⁴ throughR⁵ are hydrogen, R is methyl and R³ is propyl. It is to be alsounderstood that the siloxane polymers of this invention may contain anyone of the various types of M⁴ and D⁴ siloxy units illustrated above orany combination thereof.

In the silicon-bonded morpholino groups ##STR12## (group E³ above) theR⁴ through R⁷ groups are, as previously defined, hydrogen or C₁ to C₄alkyls. Usually, no more than two are alkyls as in the2,6-dimethylmorpholino nucleus. Preferably, each of R⁴, R⁵, R⁶ and R⁷ ishydrogen. The R⁸ and R⁹ groups are alkylene radicals, of the series,--C_(u) H_(2u) -- and --C_(v) H_(2v) --, respectively, where u is aninteger having a value from 2 to 4 (R⁸) and v is an integer having avalue from 2 to 6 (R⁹). Illustrative of the linear and branched bivalentalkylene radicals encompassed by R⁸ and R⁹ are: ethylene; 1,3-propylene; 1,2-propylene; 1,4-butylene; 1,2-butylene; 2,3-butylene;and, in addition R⁹ can be 1,5-pentylene, 1,2-pentylene, 1,6-hexyleneand the like. Preferably, --R⁸ -- has from 2 to 3, and R⁹ has from 2 to4, carbon atoms. It is to be understood that when t of themorpholino-bearing group has an average value from about 1 to about 4,--(R⁸ O)_(t) -- may be ethyleneoxy, poly(ethyleneoxy), propyleneoxy,poly(propyleneoxy), or a combination of different alkyleneoxy units.

Illustrative of such preferred M⁵ and D⁵ siloxy units are ##STR13## andthe like. The most preferred D⁵ siloxy unit being one wherein R⁴ throughR⁷ are hydrogen, R is methyl, R⁹ is propylene, and s and t are 0. It isto be understood that the siloxane polymers of this invention maycontain any one of the various types of M⁵ and D⁵ siloxy unitsillustrated above or any combination thereof.

Of the preferred acrylonitrile-capped polyoxyalkylene polysiloxanepolymers of this invention having utility as stabilizers of flexiblepolyester polyol-based urethane produced with a flame retardant arethose with the scope of Formula (I-B), and (I-G) wherein R is a methylradical; x has an average value of about 0.5 to about preferably 1 toabout 10; y has an average value of about 0.5 to about 30 preferablyabout 1 to about 10; z has an average value of about 0.5 to about 20,preferably about 1 to about 10; and the acrylonitrile-cappedpolyoxyalkylene radical (Q), is preferably

    --CH.sub.2 CH.sub.2 CH.sub.2 (OC.sub.3 H.sub.6).sub.n (OC.sub.2 H.sub.4).sub.m OCH.sub.2 CH.sub.2 CN

wherein n has an average value of 0 to 10, preferably O and m has anaverage value of from about 4 to about 30, preferably about 4 to 15; andthe cyano-containing group (E), is preferably

    --R.sup.2 CN

wherein R² is an alkylene radical having from 2 to 4 carbon atoms,preferably propylene.

The most preferred of all of the acrylonitrile-cappedpolyoxyalkylene-polysiloxane polymers of this invention are those havingthe average formula ##STR14## wherein x and y have a value of about 1 toabout 10 and m has a value of about 4 to about 15.

The acrylonitrile-capped polyoxyalkylene-polysiloxane polymers of thisinvention are prepared by the platinum catalyzed hydrosilation of theacrylonitrile-capped polyoxyalkylene compounds of this invention asdefined above with silicon-hydrogen containing siloxane startingmaterials as illustrated e.g. by the following equation ##STR15##

In which R, R', E^(o), a, b, c, d, e, f, n, m and q are the same asdefined above.

More particularly, by way of example, the most preferredacrylonitrile-capped polyoxyalkylene-polysiloxane compounds of FormulaI-A above may be illustrated by the following equation ##STR16## whereinx and y have a value of about 1 to 10 and m has a value of about 4 to15.

This general hydrosilation reaction it conventional and well known inthe art. Particularly effective is platinum in the form ofchloroplatinic acid dissolved if desired, in a solvent such astetrahydrofuran, ethanol, butanol, 1,2-dimethoxyethane or mixed solventssuch as ethanol/1,2-dimethoxyethane, It is to be understood, however,that other platinum derivatives known to the art as hydrosilationcatalysts may also be used. For example, also suitable as promoters ofthe hydrosilation reaction are the platinum catalysts prepared byreaction of chloroplatinic acid and an alcohol such as octanol asdescribed in U.S. Pat. No. 3,220,972. The platinum is present in acatalytic amount such as, for example, from about 5 to about 400 partsby weight per million (p.p.m.) parts of the combined weight of thesilicon-containing and organic reactants. The more usual platinumconcentration is no more than about 200 p.p.m. preferably 5 to 50 p.p.m.The preferred temperature range for the reaction is 60° to 138° C. Lowertemperatures may be used but the reaction times are slower. Highertemperatures may also be used up to 200° C. In carrying out the processto prepare the siloxane polymers of this invention it is generallypreferred to mix all the ingredients, except the platinum catalyst, atabout 25° C. and allow the mixture to warm up to 80° C. (with externalheating) At this temperature the platinum catalyst is added and usuallyan exothermic reaction is observed. The hydrosilation reaction may beconducted in the absence or presence of a solvent. Of course, solventswhich themselves are reactive with SiH under the conditions of thisinvention should not be employed. Illustrative solvents are normallyliquid aromatic hydrocarbons such as benzene, toluene and xylene;alcohols such as methanol, ethanol, n-propanol, isopropanol; ethers;ether alcohols; and the like. The solvents may be used individually orin combination with one another. Upon completion of the reaction, excessreactant and any organic solvent employed in the polymer preparation,may be removed by conventional separation techniques to obtain the finalproduct comprising the polymer compositions of the invention. It is tobe understood, however, that some portion or all of the solvent andexcess reactants including by-products thereof and the polyetherreactant may remain in the product and that such diluted polymercompositions are within the scope and may be used in accordance with theteachings of this invention. In the hydrosilation reaction, the removalor neutralization of the platinum catalyst is usually desirable for longrange product stability. Neutralization is readily effected by addingsodium bicarbonate to the reaction mixture followed by filtration of theresultant slurry to remove the neutralizing agent and platinum residues.The hydrosilation reaction comprising the addition of Si--H to therespective acrylonitrile-capped polyoxyalkylene compounds of thisinvention is carried out by employing said respectiveacrylonitrile-capped polyoxyalkylene compounds in an amount at leastsufficient to react with a predetermined proportion of thesilicon-bonded hydrogen of the SiH reactant. From the standpoint of moreeffective and more complete reaction of silanic hydrogen theacrylonitrile-capped polyoxyalkylene compounds are usually employed inexcess of stoichiometric requirements e.g. the acrylonitrile-cappedpolyoxyalkylene compounds may be employed in amounts up to a 100 or moremole percent excess.

The silicon-hydrogen containing siloxanes used as starting materials inthe hydrosilation reaction of this invention and/or methods for theirpreparation are well known in the art. For example, such siloxanestarting materials can be produced by cohydrolyzing and condensing theappropriate hydrolyzable silanes or by equilibrating appropriatesiloxanes using conventional techniques. Obviously the particularsiloxane starting material used in a given hydrosilation process willcorrespond to and merely depend upon the particular type ofacrylonitrile-capped polyoxyalkylene-polysiloxane product desired.

For instance the siloxane products of Formulas (I-A), (I-B), (I-C),(I-D) and (I-E) above can be produced by reacting the above-definedacrylonitrile-capped polyoxyalkylene compounds of this invention withthe following silicon-hydrogen containing starting materials,respectively ##STR17## wherein R, x and y are the same as defined above.Such starting materials are well known in the art.

The siloxane products of Formulas (I-F)and (I-G) above can be producedby reacting the above defined acrylonitrile-capped polyoxyalkylenecompounds of this invention with the following silicon-hydrogencontaining siloxane starting materials, respectively ##STR18## whereinR, E, x, y and z are the same as defined above. Such starting materialsas well as others may be produced, e.g., as disclosed in U.S. PatentApplication Ser. No. 457,510 filed Apr. 3, 1974, now U.S. Pat. No.3,954,824.

The siloxane products of Formulas (I-H)and (I-I) above can be producedby reacting the above defined acrylonitrile-capped polyoxyalkylenecompounds of this invention with the following silicon-hydrogencontaining siloxane starting materials, respectively, ##STR19## whereinR, E¹, x, y and z are the same as defined above. Such starting materialsas well as others may be produced e.g., as disclosed in U.S. PatentAppliction Ser. Nos. 536,874 and 536,884 both filed Dec. 27, 1974, nowU.S. Pats. Nos. 3,943,156 and 3,979,419 respectively.

The siloxane products of Formulas (I-J) and (I-K) above can be producedby reacting the above defined acrylonitrile-capped polyoxyalkylenecompounds of this invention with the following silicon-hydrogencontaining siloxane starting materials, respectively, ##STR20## whereinR, E², x y and z are the same as defined above. Such starting materialsas well as others may be produced e.g., as disclosed in U.S. patentapplication Ser. No. 592,129 filed June 30, 1975.

The siloxane products of Formulas (I-L) and (I-M) above can be producedby reacting the above defined acrylonitrile-capped polyoxyalkylenecompounds of this invention with the following silicon-hydrogencontaining siloxane starting materials, respectively ##STR21## whereinR, E³, x y and z are the same as defined above. Such starting materialsas well as others may be produced e.g. as disclosed in U.S. patentapplication Ser. No. 552,996 filed Feb. 25, 1975, now U.S. Pat. No.4,018,723.

The siloxane products Formula (I-N) above can be produced by reactingthe above defined acrylonitrile-capped polyoxyalkylene compounds of thisinvention with the following silicon-hydrogen containing siloxanestarting materials. ##STR22## wherein R, g, h and i are the same asdefined above. Such starting materials as well as others may be producede.g., as disclosed in U.S. Pat. Nos. 3,793,360 and 3,833,512.

The siloxane products of Formula (I-O) above can be produced by reactingthe above defined acrylonitrile-capped polyoxyalkylene compounds of thisinvention with the following silicon-hydrogen containing siloxanestarting materials. ##STR23## wherein R, j, k and p are the same asdefined above. Such starting materials as well as others may be producede.g. as disclosed in U.S. Pat. No. 3,796,676.

The acrylonitrile-capped polyoxyalkylene-polysiloxane polymers of thisinvention are normally liquid compositions and as previously describednormally comprise mixtures of polymer species which may differ inmolecular weight, polyether and siloxane contents and relative number ofmonomeric units. It is to be understood that two or more polymers or twoor more silicon-hydrogen polymers having a particular averagecomposition encompassed by respective Formulas I and II may be admixedin suitable relative proportions to adjust the average values of x, yand z as desired. For example, a siloxane polymer wherein y has anaverage value of about 5 may be admixed with another wherein y has anaverage value of about 2 to provide a siloxane polymer wherein y has anaverage value of about 3.5. Similarly a silicon-hydrogen containingsiloxane in which no R₂ SiO2/2 units are present (that is in which x is0) may be admixed in any relative proportion with another in which x is1, thereby providing a siloxane in which the average value of x is lessthan 1 (such as 0.5 etc.) which is then reacted as described herein toprovide the acrylonitrile-capped polyoxyalkylene-polysiloxane polymer inwhich x has a corresponding average value. It is to be also understoodthat a small percentage (on the average, usually about 15 mole percentor less preferably less than 10 mole percent) of theacrylonitrile-capped polyoxyalkylene blocks of the siloxane polymer maycomprise residual, uncapped hydroxyl-terminated groups introduced withthe acrylonitrile-capped polyoxyalkylene reactants. Likewise, it isunderstood that the acrylonitrile-capped polyoxyalkylene-polysiloxanepolymers of this invention may be graft or block polymers and that itmay be possible for some polymers to contain a small portion of residualunreacted Si--H groups.

The acrylonitrile-capped polyoxyalkylene-polysiloxane polymers of thisinvention are generally useful as surfactants and find particularapplication in the manufacture of urethane foam. The normally liquidpolymers can be used as such, for stabilization of urethane foam withoutthe need for combination with other surfactants or other type of organicadditive. The polymers can be employed as a 100 percent active stream,or they can be employed in dilute form as a solution in polar solvents(e.g., glycols) or non-polar organic solvents such as normally liquidaliphatic and aromatic unsubstituted and halogen-substitutedhydrocarbons (e.g., heptane, xylene, toluene, chlorobenzenes and thelike).

In addition to the acrylonitrile-capped polyoxyalkylene-polysiloxanepolymers of this invention used as foam stabilizers, the other essentialtypes of components and reactants employed in the production of urethanefoam in accordance with the process of this invention are an organicpolyol comprising a polyether polyol or a polyester polyol, an organicpolyisocyanate, an amine catalyst and a blowing agent. Thefoam-producing reaction mixtures may also contain a flame-retardant. Theamount of the acrylonitrile-capped polyoxyalkylene-polysiloxane polymersof this invention present in the final foam-producing reaction mixturemay vary over a relatively wide range such as from about 0.1 to about 5parts by weight per 100 parts by weight of the polyol reactant, and areusually present in an amount of at least about 0.2 and no more thanabout 3 parts.

In producing polyether polyol-based urethanes one or more polyetherpolyols is employed for reaction with the polyisocyanate reactant toprovide the urethane linkage. Such polyether polyols as well as methodsfor their manufacture are well known in the art and contain an averageof at least two, and usually not more than six, hydroxyl groups permolecule and include compounds which consist of carbon, hydrogen andoxygen and compounds which also contain phosphorus, halogen and/ornitrogen.

Among the suitable polyether polyols that can be employed are thepoly(oxyalkylene) polyols, that is, alkylene oxide adducts of water or apolyhydric organic compound as the initiator or starter such asdisclosed e. g. in U.S. Pat. No. 3,846,462. Illustrative of suitablepolyhydric organic initiators are any one of the following which may beemployed individually or in combination; ethylene glycol, diethyleneglycol; propylene glycol; 1,5-pentanediol; hexylene glycol; dipropyleneglycol; trimethylene glycol; 1, 2-cyclohexanediol; 3-cyclohexane-1,1-dimethanol and the 3, 4-dibromo-derivative thereof; glycerol; 1,2,6-hexanetriol; 1, 1, 1-trimethylolethane; 1, 1, 1-trimethylolpropane;3-(2-hydroxyethoxy)- and 3-(2-hydroxypropoxy)-1, 2-propanediols; 2,4-dimethyl-2-(2-hydroxyethoxy)methylpentanediol-1, 5; 1, 1,1-tris[(2-hydroxyethoxy)methyl]ethane; 1, 1.1-tris[(2-hydroxypropoxy)methyl]propane; pentaerythritol; sorbitol;sucrose, alpha-methyl glucoside; and other such polyhydric compoundsconsisting of carbon, hydrogen and oxygen and having usually not morethan about 15 carbon atoms per molecule. The alkylene oxides usuallyemployed in providing the polyether polyol reactants are the loweralkylene oxides, that is, compounds having from 2 to 4 carbon atomsincluding ethylene oxide, propylene oxide, butylene oxides (1, 2- or2,3-) and combinations thereof.

Another class of polyether polyols are polymer/polyether polyols whichare also well known in the art. Such reactants are produced bypolymerizing one or more ethylenically unsaturated monomers dissolved ordispersed in a polyether polyol in the presence of a free radicalcatalyst. Illustrative of suitable ethylenically unsaturated monomersare those encompassed by the formula ##STR24## where: R^(ooo) ishydrogen, methyl or any of the halogens (i.e., fluorine, chlorine,bromine or iodine); and R^(oooo) is R^(ooo), cyano, phenyl,methyl-substituted phenyl, or alkneyl radicals having from 2 to 6 carbonatoms such as vinyl, allyl and isopropenyl groups. Typical examples ofsuch polymerizable monomers are the following which may be employedindividually or in combination; ethylene, propylene, acrylonitrile,methacrylonitrile, vinyl chloride, vinylidene chloride, styrene,alpha-methylstyrene, and butadiene. These and other polymer/polyolcompositions which are suitably employed either individually or incombination with each other or with poly)oxyalkylene)polyols are thosedescribed in British patent specification No. 1,063,222 and U.S. Pat.No. 3,383,351, the disclosures of which are incorporated herein byreference thereto.

The particular polyether polyol or mixtures thereof employed merelydepend upon the end-use of the polyurethane foam desired. Usually diolsprovide soft foams. Firmer foams are obtained by the incorporation ofpolyether polyols having more than two hydroxyl groups, includingtriols, tetraols, pentols and hexols. When it is desired to producepolyurethanes having comparatively high load-bearing properties and/ordiecutability, polymer/polyether polyols of the aforesaid type are used.In the production of flexible polyurethane foams the hydroxyl number ofthe polyether polyol reactant including mixtures of polyols may varyfrom about 20 to about 150 and is usually no higher than about 80.

More particularly this invention is directed to the production ofpolyester polyol-based urethane foam, especially flexible polyesterpolyurethane foam which most preferably also contains a flame retardingagent. As indicated above the acrylonitrile-cappedpolyoxyalkylene-polysiloxane polymers of this invention intended for useas stabilizers of polyester polyol-derived foam can be used as suchwithout the need for combination with an anionic or cationic organicsurfactant or other type of organic additive.

However, it is often the preferred practice of foam manufacturers topremix the foam stabilizer, amine catalyst and water (which is the usualsource of at least part of the blowing action) and to feed the aqueouspremixture to the polyester foam-producing reaction mixture as a singlestream. Thus, it is desirable to employ the acrylonitrile-cappedpolyoxyalkylene-polysiloxane polymer foam stabilizers of this inventionin solution in combination with an organic acidic component, a watersoluble organic surfactant and/or a water soluble glycol in order toavoid premix incompatibility. Although these various organic additivescan be introduced directly to the aqueous premixture of foam stabilizerand catalyst, the formation of clear homogeneous aqueous solutions isfacilitated by blending the additives with the foam stabilizer (that isthe acrylonitrile-capped polyoxyalkylene-polysiloxane polymers of thisinvention) and combining the resulting blend with water and the aminecatalyst system.

Thus, in accordance with another embodiment of this invention,therefore, solution compositions are provided comprising theacrylonitrile-capped polyoxyalkylene-polysiloxane polymers of thisinvention, the aforesaid organic acid component, and one or both of anorganic surfactant and glycol. The acrylonitrile-cappedpolyoxyalkylene-polysiloxane polymers of this invention may be presentin the solution compositions in an amount of from about 10 to about 80parts by weight per 100 parts by weight of the solution. Suitableorganic acidic components, organic surfactants and glycols for thispurpose are as described in U.S. Pat. Nos. 3,793,360 and 3,833,512, thedisclosures of which are incorporated herein by reference thereto.

For instance the aforesaid organic acidic comonent comprises thesaturated and unsaturated aliphatic and cycloaliphatic carboxylic acidscontaining from 15 to 20 carbon atoms. Illustrative of suitable acidiccomponents are the fatty acids such as, for example, palmitic, stearic,palmitoleic, oleic, linoleic, linolenic and ricinoleic acids; resinacids of the abietic and pimaric type; and any combination of theaforesaid acids as well as industrial by-products andnaturally-occurring materials comprising such acids. An especiallysuitable acidic component of the solution compositions and aqueouspremixtures of this invention is tall oil which is a by-product ofsulfate digestion of wood pulp and is composed largely of fatty acids(oleic, linoleic, linolenic and palmitic acids) and resins acids, and aminor amount of neutral material such as fatty acid esters.

The above-described organic acidic component can be present in thesolution compositions of this invention in an amount of from about 5 toabout 90 parts by weight per 100 parts by weight of silicone polymerpresent in the solution.

The water-soluble organic surfactant which can be a component of thesolution compositions of this invention may be of the nonionic, anionic,cationic or amphoteric types, including combinations thereof.Preferably, the organic surfactant is a nonionic surfactant such as: thepoly)oxyalkylene) ethers of the higher alcohols having from 10 to 18carbon atoms including mixtures thereof; polyoxyalkylene ethers ofalkyl-substituted phenols in which the alkyl group can have from 6 to 15carbon atoms; and corresponding polythioalkylene adducts of theaforesaid higher alcohols and phenols. The length of the ether chain issuch that appropriate hydrophilic character is provided to balance thehydrophobic portion derived from the alcohol or phenol and render thecompound soluble in water. The chain may contain oxyethylene unitseither as essentially the sole type of unit or oxyethylene incombination with a minor amount of oxypropylene. It is preferred thatthe hydrophilic portion of the nonionic surfactants be composedessentially of oxyethylene monomeric units. Usually the average numberof such --OC₂ H₄ -- units ranges from about 4 to about 20, althoughupwards of 40 such units can also be present.

Typical examples of nonionic surfactants which can be used as componentsof the solution compositions of this invention are the adducts producedby reaction of k moles of ethylene oxide (wherein k has a value of fromabout 4 to about 40, inclusive of whole and fractional numbers) per moleof any of the following hydrophobes including mixtures thereof;n-undecyl alcohol, myristyl alcohol, lauryl alcohol, trimethyl nonanol,tridecyl alcohol, pentadecyl alcohol, cetyl alcohol, oleyl alcohol,stearyl alcohol, nonylphenol, dodecylphenol, tetradecylphenol, and thelike.

Other illustrative water soluble organic surfactants which can bepresent as a component of the solution compositions of this inventionare: sodium, potassium ammonium and quaternary ammonium salts ofsulfonic acids wherein the hydrocarbyl portion can be alkyl or alkarylgroups containing from 10 to 20 carbon atoms. Examples of such organicsurfactants are: sodium tetradecyl sulfonate and sodium dodecylbenzenesulfonate; sodium and potassium salts of sulfonated petroleum fractionssuch as mineral oil; diethylamine salts of sulfonated C₁ -C₁₅ alkylatedaromatic hydrocarbons; taurine compounds having at least one long chainhydrocarbyl group bonded to nitrogen; and the like.

The solution compositions of this invention may also contain as a thirdtype of organic component, a glycol of from 2 to about 10 carbon atoms,or low molecular weight Carbowax polyethylene glycols. Especiallysuitable is hexylene glycol (2-methyl-2,4-pentanediol).

When both the organic surfactant and glycol components are present inthe solution compositions of this invention, the combinatedconcentration thereof ranges from about 5 to about 90 parts by weightper 100 parts by weight of the silicon polymer contained herein. Whenonly one of these components is present, the concentration thereof isalso within this latter range.

When the aforesaid solution compositions of the silicone polymers ofthis invention are combined water and amine catalyst such as thecatalysts described hereinbelow, clear, homogeneous aqueous solutionsare obtained which can be added directly to the foam-producing reactionmixture. From the standpoint of retaining these desirablecharacteristics of clarity and homogeneity under otherwise adverseambient temperatures which may be encountered upon standing, storage orshipment prior to use in the foam-producing reaction, the preferredaqueous premixtures are those containing both the organic surfactant (ofwhich nonionics are preferred) and the glycol, in addition to theorganic acidic component. It is to be understood that the aforesaidinvention are also useful when added directly to the finalfoam-producing reaction mixture rather than being premixed with waterand amine catalyst.

In producing polyester polyol-based urethanes one or more polyesterpolyols is employed for reaction with the polyisocyanate reactant toprovide the urethane linkage. Such polyester polyols as well as methodsfor their manufacture are well known in the art as seen for example, byU.S. Pat. No. 3,793,360. For instance, polyester polyols employed inproducing flexible polyester urethane foams in accordance with themethod of this invention are the reaction products of: (1) apolyfunctional organic carboxylic acid, and (2) one or more of theaforesaid polyether polyols or one or more of the aforesaid polyhydricorganic initiators which are reacted with alkylene oxide to produce suchpolyether polyols. The polyester polyols contain at least two hydroxylgroups per molecule (as alcoholic OH or as OH in COOH groups). Thefunctionality of these acids si preferably provided by carboxy groups(COOH) or by both carboxy groups and alcoholic hydroxyl groups. Thepolyesters can have hydroxyl numbers from about 20 to about 150, andpreferably have hydroxyl numbers between about 35 and about 80. Thesehydroxyl numbers are readily determined according to the proceduredescribed by Mitchel et al., Organic Analysis Vol. I (IntersciencePublishers, New York 1953). Typical of the polyfunctional organiccarboxylic acids that can be employed in producing polyester polyolsuseful in preparing the foams of this invention are: dicarboxylicaliphatic acids such as succinic, adipic, sebacic, azelaic, glutaric,pimelic, malonic and suberic acids; and dicarboxylic aromatic acids suchas phthalic acid, terephthalic acid, isophthalic acid and the like.Other polycarboxylic acids that can be employed are the "dimer acids"such as the dimer of linoleic acid. Hydroxyl-containing monocarboxylicacids (such as ricinoleic acid) can also be used. Alternatively, theanhydrides of any of these various acids can be employed in producingthe polyester polyols. The polyhydric alcohols (organic polyols) thatcan be employed in producing the polyester polyol starting material usedin the process of this invention include the monomeric polyhydricalcohols such as for example, glycerol; 1,2,6-hexanetriol; ethyleneglycol; diethylene glycol; trimethylol propane; trimethylolethane;pentaerythritol; propylene glycol; 1, 2-, 1,3- and 1,4-butylene glycols;1,5-pentanediol; sorbitol; and the like, including mixtures thereof.

Other polyhydric alcohols that can be employed in producing thepolyester polyols useful in this invention are the polymeric polyhydricalcohols which include the linear and branched chain polyethers having aplurality of acyclic ether oxygens and at least two alcoholic hydroxylradicals. Illustrative of such polyether polyols are thepoly(oxyalkylene) polyols containing one or more chains of connectedoxyalkylene radicals which are prepared by the reaction of one or morealkylene oxides with acyclic and alicyclic polyols. Examples of thepoly(oxyalkylene) polyols include the poly(oxyethylene) glycols preparedby the addition of ethylene oxide to water, ethylene glycol ordiethylene glycol; glycols prepared by the addition of propylene oxideto water, propylene glycol or dipropylene glycol; mixedoxyethylene-oxypropylene polyglycols prepared in a similar mannerutilizing a mixture of ethylene oxide and propylene oxide or asequential addition of ethylene oxide and propylene oxide; and thepoly(oxybutylene)glycols and copolymers such aspoly(oxyetheylene-oxybutylene) glycols andpoly(oxypropylene-oxybutylene) glycols. Included in the term"poly(oxybutylene) glycols" are polymers of 1,2- butyleneoxide and2,3-butyleneoxide.

Illustrative of further polyester polyol reactants that are useful inproducing flexible polyester urethane foam in accordance with theprocess of this invention are the reaction products of any of theaforesaid polycarboxylic acids and the polyhydric alcohols prepared bythe reaction of one or more alkylene oxides such as ethylene oxide,propylene oxide, butylene oxide and mixtures thereof, with any of thefollowing: glycerol; trimethylolpropane; 1,2,6-hexanetriol;pentaerythritol; sorbitol; glycosides such as methyl, ethyl, propyl,butyl and 2-ethylhexyl arabinoside, xyloside, fructoside, glucoside, andrhammoside; sucrose; mononuclear polyhydroxylbenzenes such asresorcinol, pyragallol, phloroglucinol, hydroquinone,4,6-di-tertiary-butylcatechol, and catechol; polynuclearhydroxylbenzenes("polynuclear" designating at least two benzene nuclei)such as the di-, tri- and tetra-phenylol compounds in which two to fourhydroxybenzene groups are attached either directly by means of singlebonds or through an aliphatic hydrocarbon radical containing 1 to 12carbon atoms, such compounds being typically illustrated by2,2-bis(p-hydroxyphenyl)-propane, bis(p-hydroxyphenyl)-methane and thevarious diphenols and diphenol methanes disclosed in U.S. Pat. Nos.2,506,486 and 2,744,882, respectively. Another type of polyester polyolreactant is that produced by reaction of a polycarboxylic acid and thepolyether adducts formed by reaction of ethylene oxide, propylene oxideor butylene oxide with phenol-formaldehyde condensation products such asthe novolaks.

The organic polyisocyanates that are useful in producing polyether andpolyester foam in accordance with the process of this invention areorganic compounds that contain at least two isocyanato groups. Suchcompounds are well known in the art for producing polyurethane foams andare conveniently represented by the general formula

    Q'(NCO).sub.i

wherein i is an integer of 2 or more and Q' is an organic radical havingthe valence of i. Q' can be a substituted or unsubstituted hydrocarbongroup (e.g. alkylene, cycloalkylene, arylene, alkarylene, aralkylene andthe like). Q' can also be a group having the formula Q"--Z'--Q" whereinQ" is an alkylene or arylene group and Z' is a divalent moiety such as--O--, --O--Q"--O--, --C(O)--, --S--, --S--Q"--S--, or --SO₂ --.

Illustrative of suitable organic polyisocyanate reactants are thefollowing including mixtures thereof:

1,12-diisocyanato-ethane;

1,3-diisocyanato-propane;

1,4-diiocyanato-butane;

1,5-diisocyanato-pentane;

1,6-diisocyanato-hexane;

1,5-diisocyanto-2,2-dimethyl-pentane;

1,7-diisocyanato-heptane;

1,5-diisocyanato-2,2,4-trimethyl-pentane;

1,8-diisocyanato-octane;

1,9-diisocyanato-nonane;

1,10-diisocyanato-decane;

1,11-diisocyanato-undecane;

1,12-diisocyanato-dodecane;

1,6-diisocyanato-3-methoxy-hexane;

1,6-diisocyanato-3-butoxy-hexane;

bis(3-isocyanato-propyl)ether

the (bis(3-isocyanato-propyl)ether of 1,4-butylene glycol;

(OCNCH₂ CH₂ CH₂ OCH₂)₂ O;

bis(2-isocyanatoethyl)carbonate;

1-methyl-2,4-diisocyanato-cyclohexane;

1,8-diisocyanato-p-methane;

mixtures of 2,4-and 2,6-tolylene-diisocyanate;

2,4-tolylene-diisocyanate;

2,6-tolylene-diisocyanate;

crude tolylene-diisocyanates;

bis-5-6(2-isocyanatoethyl)bicyclo[2.2.1]hept-2-ene;

bis(3-isocyanato-propyl)sulfide;

bis(isocyanato-hexyl)sulfide;

1,4-phenylene-diisocyanate;

xylylene diisocyanates;

4-chloro-1,3-phenylene-diisocyanate;

4-bromo-1,3-phenylene-diisocyanate;

4-nitro-(1,3 or 1,5)-phenylene-diisocyanate;

4-ethoxy-1,3-phenylene-diisocyanate;

benzidine diisocyanate;

toluidine diisocyanate;

dianisidine diisocyanate;

2,4'- or 4,4'-diisocyanato-diphenyl ether;

diphenylmethane-4,4'-diisocyanate;

4,4'-dissocyanato-dibenzyl;

isopropyl-benzene-alpha-4-diisocyanate;

1,5-diisocyanato-naphthalene;

1,8-diisocyanato-naphthalene;

9,10-diisocyanato-anthracene;

triphenylmethane-4,4'4"-triisocyanate;

2,4,6-toluene triisocyanate;

and many other organic polyisocyanates that are known in the art such asthose disclosed in an article by Siefken, Ann., 567, 75 (1949). Ingeneral, the aromatically unsaturated polyisocyanates are preferred.

Further included among the isocyanates useful in the process of thisinvention are dimers and trimers of isocyanates and diisocyanates andpolymeric diisocyanates such as those having the general formula:

    [Q(NCO).sub.i ].sub.j

in which i and j are integers of 2 or more and/or (as additionalcomponent in the reaction mixtures) compounds of the general formula:

    L'(NCO).sub.1

in which i is 1 or more and L' is a monofunctional or polyfunctionalatom or radical. Examples of this type include ethylphosphonicdiisocyanate, C₂ H₅ P(O)(NCO)₂ ; phenylphosphonic diisocyanate, C₆ H₅P(O)(NCO)₂ ; compounds containing an .tbd.Si--NCO group, isocyanatesderived from sulfonamides (QSO₂ NCO), cyanic acid, thiocyanic acid, andcompounds containing a metal--NCO radical such as tributyltinisocyanate.

Also included as useful in the preparation of the flexible polyesterurethane foams in accordance with the process of this invention are thepolyisocyanates of the aniline-formaldehyde polyaromatic type which areproduced by phosgenation of the polyamine obtained by acid-catalyzedcondensation of aniline with formaldehyde. Poly(phenylmethylene)polysiocyanates of this type are available commercially under such tradenames as PAPI, AFPI, Mondur MR, Isonate 390 P, NCO-120 and NCO-20. Theseproducts are low viscosity (50-500 centipoises at 25° C.) liquids havingaverage isocyanato functionalities in the range of about 2.25 to about3.2 or higher, depending upon the specific aniline-to-formaldehyde molarratio used in the polyamine preparation.

Other useful polyisocyanates are combinations of diisocyanates withpolymeric isocyanates containing more than two isocyanto groups permolecule. Illustrative of such combinations are: a mixture of2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and the aforesaidpoly(phenylmethylene) polyisocyanates; and a mixture of isomerictolylene diisocyanates with polymeric tolylene diisocyanates obtained asresidues from the manufacture of the diisocyanates.

On a combined basis, the polyether or polyester polyol and organicpolyisocyanate usually constitute the major proportion by weight of thepolyurethane-forming reaction mixture. In general, the polyisocyanateand polyol reactants are employed in relative amounts such that theratio of total --NCO equivalents to total active hydrogen equivalent (ofthe polyol and any water, when used) is from about 0.8 to about 1.5,preferably from about 0.9 to about 1.2, equivalents of --NCO perequivalent of active hydrogen. This ratio is known as the IsocyanateIndex and is often also expressed as a percent of the stoichiometricamount of polyisocyanate required to react with total active hydrogen.When expressed as a percent, the Isocyanate Index may be from about 80to about 150, and is preferably within the range from about 90 to about120.

The urethane-forming reaction is effected in the presence of a minoramount of a catalyst comprising an amine. This component of thepolyurethane-forming reaction mixture is usually a tertiary-amine asdisclosed for example in U.S. Pat. No. 3,793,360. Suitable aminecatalysts include one or more of the following: N-methyl-morpholine;N-ethylmorpholine; N-octadecylmorpholine; triethylamine; tributylamine;trioctylamine; N,N,N',N'-tetramethylethylenediamine;N,N,N',N'-tetramethyl-1,3-butanediamine; triethanolamine;N,N-dimethylethanolamine; triisopropanolamine; N-methyldiethanolamine;hexadecyldimethylamine; N,N-dimethylbenzylamine; trimethylamine;bis[2-(N,N-dimethylamino)ethyl]ether; triethylenediamine (i.e.,1,4-diazabicyclo[2.2.2.]octane); the formate and other salts oftriethylenediamine; oxyalkylene adducts of the amino groups of primaryand secondary amines and other such amine catalysts which are well knownin the art of polyurethane manufacture. Also useful are thebeta-tertiary amino amides and esters described in U.S. Pat. No.3,821,131, as exemplified by3-(N,N-dimethylamino)-N',N'-dimethylpropionamide. Also useful as theamine catalyst are the beta-tertiary-amino nitriles described incopending application Ser. No. 369,556, filed June 13, 1973, now U.S.Pat. No. 3,925,268, such as in particular,3-(N,N-dimethylamino)propionitrile as such or in combination with othertertiary amines such as bis-[2-N,N-dimethylamino)ether]ether. The aminecatalyst may be introduced to the polyurethane-producing reactionmixture as such or as a solution in suitable carrier solvents such asdiethylene glycol, dipropylene glycol, and 2-methyl-2,4-pentanediol("hexylene glycol"), and the like.

The amine catalyst is present in the final urethane-producing reactionmixture in a catalytic amount such as from about 0.05 to about 8 partsby weight of active catalyst (that is, the amine exclusive of othercomponents present in solutions thereof) per 100 parts by weight of thepolyol reactant. In forming polyether polyol urethane foam, the aminecatalyst concentration is usually no higher than about 3 parts. Informing polyester polyol urethane foam, the preferred concentration oftotal amine catalyst is a least about 0.2 up to about 8 parts, althoughmore than about 5 parts is usually not required.

In producing polyurethane from polyether polyols the usual practice isto include as a further component of the reaction mixture a minor amountof certain metal catalysts which are useful in promoting gellation ofthe foaming mixture. Such supplementary catalysts are well known to theart of flexible polyether-based polyurethane foam manufacture. Forexample, useful metal catalysts include organic derivatives of tin,particularly stannous salts of carboxylic acids, dialkyltindicarboxylates, polyalkyl tin oxides and tin mercaptides. Typical ofsuch cocatalysts are stannous octoate, stannous oleate, stannousacetate, stannous laurate and dibutyltin dilaurate. Additional metalcatalysts are organic derivatives of other polyvalent metals such aszinc and nickel (e.g., nickel acetylacetonate). In general, the amountof such metal co-catalysts which can be present in thepolyurethane-producing reaction mixture is within the range from about0.05 to about 2 parts by weight per 100 parts by weight of the polyetherpolyol reactant. Although such metal catalysts are suitably employed inthe preparation of polyether polyol urethane foam, their use isgenerally avoided in the manufacture of foam derived from a polyesterpolyol.

The amine catalyst may also be used in combination with other additivessuch as any of the nonionic organic surfactants described above inconnection with the solution compositions of this invention. Examples ofnon-ionics which are especially useful as components of the catalystsolutions are the oxyethylated nonylphenol compounds represented by thegeneral formula

    C.sub.9 H.sub.19 --C.sub.4 H.sub.4 --(OC.sub.2 H.sub.4).sub.k --OH

wherein k is a number having an average value of from about 9 up toabout 20 or more, including average values of k which are either wholeor fractional numbers such as 9, 10.5, 15 and the like. When used, thenon-ionic organic surfactant may be present in an amount from about 10to about 80 weight percent, based on the total weight of the catalystsolution. The catalyst solution may also include minor amounts ofpolysiloxane-polyoxyalkylene block copolymers and/or the organosiliconepolymers of U.S. Pat. No. 3,793,360.

It is to be understood that any of the aforesaid amine catalysts orsolutions thereof can be added directly to the foam-producing reactionmixture or they can be added in premixed form with water and thepolymeric organsilicone foam stabilizers of this invention. In thelatter event, the catalyst is preferably added as a component of theabove described homogeneous aqueous premixture of this invention.

Foaming is accomplished by the presence in the reaction mixture ofvarying amounts of a polyurethane blowing agent such as water which,upon reaction with isocyanate generates carbon dioxide in situ, orthrough the use of blowing agents which are vaporized by the exotherm ofthe reaction, or by a combination of the two methods. Thus, in additionto or in place of water, other blowing agents which can be employedinclude methylene chloride, liquefied gases which have boiling pointsbelow 80° F. and above -60° F., or other inert gases such as nitrogen,carbon dioxide added as such, methane, helium and argon. Suitableliquefied gases include aliphatic and cycloaliphatic fluorocarbons whichvaporize at or below the temperature of the foaming mass. Such gases areat least partially fluorinated and may also be otherwise halogenated.Fluorocarbon blowing agents suitable for use in foaming the formulationsof this invention include trichlorofluoromethane,dichlorodifluoromethane, 1,1-dichloro-1-fluorethane,1,1,1-tribluoro-2-fluoro-3,3-difluoro-4,4,4-trifluorobutane,hexafluorocyclobutene and octafluorocyclobutane. Another useful class ofblowing agents include thermally unstable compounds which liberate gasesupon heating, such as N,N'-dimethyl-N, N'-dinitrosoterephthalamide andthe like. The generally preferred method of foaming for producingflexible foams is the use of water or a combination of water plus afluorocarbon blowing agent such as trichloromonofluoromethane.

The amount of blowing agent employed will vary with factors such as thedesired density of the foamed product. Usually, however, from about 1 toabout 30 parts by weight of the blowing agent per 100 parts by weight ofthe polyol reactant is preferred. It is to be understood, however, thatthese are general guidelines and that the choice of the particularamount of blowing agent employed to obtain a desired foam densityspecification varies from formulation to formulation and is well withinthe skill of the art to which the present invention pertains.

The organic flame retardants that can be employed in producing urethanefoam stabilized with the acrylonitrile-cappedpolyoxyalkylene-polysiloxane polymers of the invention, can bechemically combined in one or more of the other materials used (e.g., inthe polyol or polyisocyanate), or they can be used as discrete chemicalcompounds added as such to the foam formulation and are well known inthe art as seen by U.S. Pat. No. 3,793,360. The organic flame-retardantsusually contain phosphorus or halogen, both phosphorus and halogen orphosphorus and nitrogen. Usually, the halogen, when present, is chlorineand/or bromine. Flame-retardants of the discrete chemical varietyinclude: 2,2-bis(bromomethyl)-1,3-propanediol (also known asdibromoneopentyl glycol); 2,3-dibromopropanol; tetrabromophthalicanhydride; brominated phthalate ester diols such as those produced fromtetra-bromophthalic anhydride, propylene oxide and propylene glycol;tetrabromobisphenol-A; 2,4,6-tribromophenol; pentabromophenol;brominated anilines and dianilines; bis(2,3-dibromopropyl)ether orsorbitol; tetrachlorophthalic anhydride; chlorendic acid; chlorendicanhydride; diallyl chlorendate; chlorinated maleic anhydride;tris(2-chloroethyl)phosphate [(ClCH₂ CO₂ O)P(O)];tris(2,3-dibromopropyl)phosphate; tris(2,3-dichloropropyl)phosphate;tris(1-bromo-3-chloroisopropyl)phosphate;bis(2,3-dibromopropyl)phosphoric acid or salts thereof; oxypropylatedphosphoric and polyphosphoric acids; polyol phosphites such astris(dipropylene glycol) phosphite; polyol phosphonates such asbis(dipropylene glycol)hydroxymethyl phosphonate;di-poly(oxyethylene)hydroxymethyl phosphonate;di-poly(oxypropylene)phenyl phosphonate;di-poly(oxypropylene)-chloromethyl phosphonate;di-poly(oxypropylene)butyl phosphonate; andO,O-diethyl-N,N-bis(2-hydroxyethyl)-aminomethyl phosphonate. Alsosuitable are compounds having the formulas: ##STR25## which areavailable from Monsanto Chemical Company under the names Phosgard 2XC-20and Phosgard C-22-R, respectively. Other suitable flame-retardantscomprise halogen-containing polymeric resins such as polyvinylchlorideresins in combination with antimony trioxide and/or other inorganicmetal oxides such as zinc oxide, as described in U.S. Pat. Nos.3,075,927; 3,075,928; 3,222,305 and 3,574,149. Illustrative of suitableinorganic phosphorus-containing flame-retardants is the ammoniumpolyphosphate available from Monsanto Chemical Company under the namePhoscheck P30. The latter is especially useful as a flame-retardant forpolyester urethane foam. It is to be understood that otherflame-retardants known to the art may be used and that the aforesaidcompounds may be employed individually or in combination with oneanother.

Of the above flame-retardants, those of the discrete chemical compoundvariety which contain groups reactive with hydroxyl or isocyanato groupscan be used as reactants in producing the polyether polyol or polyesterpolyol or they can be reacted with organic polyisocyanates, to producecorresponding modified polyols or polyisocyanates having chemicallycombined flame-retarding groups. Such modified polyols andpolyisocyanates are also useful as reactants in the process of thisinvention. In such cases, due regard must be given to the possibleeffect of the functionality of the compound on the other properties(e.g., degree of flexibility of the resulting foam.

The flame-retarding agent can be present in the foam formulationsdescribed herein in an amount from about 1 to about 30 parts by weightper one hundred parts by weight of the polyol reactant. Usually theflame-retardant is employed in an amount of at least about 5 parts byweight per 100 parts by weight of polyol. As will be evident to thosehaving skill in the art, the particular amount of flame-retardantemployed depends largely on the efficiency of any given agent inreducing flammability of polyurethane foam.

The polyurethane foams may be formed in accordance with any of theprocessing techniques known to the art. Usually the "one-shot" processis used. In this method, the polyol and polyisocyanate reactants areindependently added to the foam-producing reaction mixture and the--OH/--NCO reaction is effected simultaneously with the foamingoperation. It is often convenient to add the foam stabilizing componentcomprising the acrylonitrile-capped polyoxyalkylene-polysiloxanepolymers of the present invention to the reaction mixture as apremixture with one or more of the blowing agent, polyol, amine catalystand, when used, the flame-retardant. The foaming and urethane-formingreactions occur without the application of external heat. Often theresulting foam is cured by heating the foam at a temperature betweenabout 100° C. and about 150° C. for about 5 to about 60 minutes toeliminate any surface tackiness, as desired. It is to be understood thatvariations in process conditions and manipulative steps can be used asknown in the art. For example, the various ingredients of the reactionmixture can be combined and the foaming reaction mixture poured into amold, or the various ingredients can be combined and the foamingreaction mixture commenced and completed in a mold.

The relative amounts of the various components present in thefoam-producing reaction mixture are not narrowly critical. The polyoland polyisocyanate are present in the foam-producing formulation in amajor amount. The relative amounts of these two components is the amountrequired to produce the urethane structure of the foam and such relativeamounts are well known in the art. The source of the blowing action suchas water, auxiliary blowing agents, catalyst and the foam stabilizer areeach present in a minor amount necessary to achieve the function of thecomponent. Thus, the blowing agent is present in a minor amountsufficient to foam the reaction mixture, the amine catalyst is presentin a catalytic amount (i.e., an amount sufficient to catalyze thereaction to produce the urethane at a reasonable rate), and theacrylonitrile-capped polyoxyalkylene-polysiloxane polymers of thisinvention are present in a foam-stabilizing amount, that is, in anamount sufficient to stabilize the foam. The preferred amounts of thesevarious components are as given hereinabove.

If desired, other additional ingredients can be employed in minoramounts in producing the polyurethane foams in accordance with theprocess of this invention. For example, the solution compositions of thesilicone polymer foam stabilizers of this invention as well as theaqueous premixtures can contain such components as inhibitors such ase.g., d-tartaric acid, tertiary-butyl pyrocatechol anddi-tert-butyl-p-cresol ("Ionol"), which reduce any tendency of thefoamed product to oxidative or hydrolytic instability. Further, when thefoam stabilizers of this invention and/or the amine catalyst areemployed as respective solutions, water soluble carrier solvents andcomponents thereof are, of course, introduced into the aqueouspremixtures without however, any deleterious affect on the effectivenessof homogeneity of the aqueous solution premixtures. Additionalillustrative additives are: cross-linking agents such as glycerol,triethanolamine and their oxyalkylene adducts; compression set additives(e.g., hexylene glycol); additives to regulate cell structure so as tocoarsen cells and hereby reduce the tendency of the foam to split (e.g.,paraffin oil); fillers; dyes; pigments; and particularly in regard topolyester polyol-derived foam, anti-discoloration additives includinganti-scorch and antioxidation agents such as phenols substituted withtertiary-butyl groups as exemplified by 2,6-di-tert-butyl-4-methylphenol("Ionol"), oxirane-containing compounds (e.g., propylene oxide),triorgano-(e.g., triphenyl-)substituted phosphites and phosphines, andother anti-discoloration additives known to the art.

The flexible urethane foams produced in accordance with this inventioncan be used in the same areas as conventional polyether and polyesterurethane foams, the products formed with a flame-retarding agent beingespecially useful where reduced combustibility properties arebeneficial. Thus, the foam products are useful as textile interliners,cushioning materials for seating and mattresses, for packaging ofdelicate objects, as gasketing materials, and the like.

As seen by the following examples the acrylonitrile-cappedpolyoxyalkylene-polysiloxane polymers of this invention possess a highlydesirable combination of properties. For instance even when employed inthe absence of additional organic surfactants they have been found to beeffective stabilizers for flexible polyester foam and further allow forthe formation of said foam having a low burning extent when said foamcontains a flame retardant. Moreover, said siloxane polymers of thisinvention can also be blended with organic surfactants which blendedsurfactants can form clear homogeneous premixes, effectively stabilizeflexible polyester foam, and further allow for the formation of saidfoam having a low burning extent when said foam contains aflame-retardant. In addition said siloxane polymers of this inventionhave excellent potency as stabilizers for flexible polyester foam andthus furnish a wide processing latitude for the production of said foam.

The following examples illustrate the present invention and are not tobe regarded as limitative. It is to be understood that all parts,percentages and proportions referred to herein and in the claims are byweight unless otherwise indicated. Moreover, as used herein thefollowing terms have the indicated significance:

In the formulas "Me" designates a methyl group, --CH₃.

"GPC" denotes that the number average molecular weight (MN) for variouspolymer compositions of this invention were measured by Gel PermeationChromatography (abbreviated in the examples as "GPC") using acalibration curve showing the relationship between the respectiveelution volumes established for dimethylsiloxane fluids of differentmolecular weights and the respective known molecular weights of suchfluids. In establishing the calibration curve, the variousdimethyl-siloxane fluids were in solution in trichloroethylene solventusing styragel packed columns. In measuring the molecular weights of thepolymers described herein, the elution volume observed for anyparticular polymer product (in trichloroethylene solvent) was equatedwith the corresponding elution volume of the calibration curve, and themolecular weight associated with that particular elution volume wasassigned as the molecular weight of the polymer product. Gel PermeationChromatography as a technique for measuring molecular weight isdiscussed in "Polymer Fractionation" (ed. Manfred J. R. Cantow, AcademicPress, Inc. New York 1967), pages 123-173, Chapter B4, entitled "GelPermeation Chromatography," by K. H. Altgelt and J. C. Moore. Indetermining the molecular weights given in the examples, the particularprocedure employed was that described in the article entitled"Characterization of Silicones by Gel Permeation Chromatography" by F.Rodriguez et al. in I & EC Product and Development, Vol. 5, No. 2, page121 (June 1966) using five styragel packed columns (Water Associates,Inc.) having a pore size of 10³ A, 3 × 10³ A, 10⁴ A, 3 × 10⁴ A, and 8 ×10³ A, respectively.

"Rise" denotes the foam height and is directly proportional to potencyof the surfactant.

"Breathability" denotes the porosity of a foam, being roughlyproportional to the number of open cells in a foam, and was measured inaccordance with the NOPCO breathability test procedure described by R.E. Jones and G. Fesman, "Journal of Cellular Plastics" (January, 1965).In accordance with this test, breathability is measured as follows: A 2inch × 2 inch × 1 inch piece of foam is cut from near the center of thebun. Using a Nopco Foam Breathability Tester, Type GP-2 Model 40GD10,air is drawn through the foam sample at a pressure differential of 0.5inches of water less than atmospheric pressure. The air flow is parallelto the direction of original foam rise. The degree of openness of thefoam (or foam breathability) is measured by the rate of air flow throughthe foam and is reported in standard cubic feet per minute (SCFM).

"CPI" denotes "cells per inch", that is, the number of cells per linearinch of the foam. CPI is directly proportional to the fineness of thecell structure. "Burning Extent" was determined in accordance withstandard flammability test procedure ASTM D-1692-68. Burning extentdenotes the burned length (in inches) of the foam and is reported as theaverage of the results obtained with the various test specimens of agiven foam. On the basis of this test, an average burning extent of lessthan 5.0 inches qualifies the foam for a self-extinguishing ("SE")rating. When the burning extent of at least one test specimen is 5.0inches or greater, the foam is assigned a burning ("B") rating andusually no further specimens of that foam are tested.

"Burning Time" denotes the average time (in seconds) taken to give thespecified burning extent.

"Top Collapse" denotes settling of the foam height upon cooling.

SURFACTANTS OF THIS INVENTION

"Surfactant AA" denotes a blended composition consisting of

    ______________________________________                                        Component           Parts by Weight                                           ______________________________________                                        Siloxane Surfactant.sup.1                                                                         52                                                        Nonionic Surfactant.sup.2                                                                         10.4                                                      Tall Oil            15.6                                                      Hexylene Glycol     21.0                                                      Ionol.sup.3         1.0                                                       ______________________________________                                         .sup.1 A siloxane polymer having the average composition formula [Me.sub.     SiO1/2].sub.1.0 [C.sub.6 H.sub.5 CH.sub.2 O(C.sub.2 H.sub.4 0).sub.7.7        C.sub.3 H.sub.6 Si(Me)O].sub.1.0 [SiO4/2].sub.0.9                             .sup.2 An organic nonionic surfactant in which the hydrophobe is a mixtur     of C.sub.11 to C.sub.15 alcohols and the hydrophile is ethylene oxide         (avg. 9 mols/mol of hydrophobe).                                              .sup.3 2,6-di-tertiary-butyl-p-cresol.                                   

"Surfactant BB" denotes a siloxane polymer having the averagecomposition formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.5 (C.sub.6 H.sub.5 CH.sub.2)(C.sub.2 H.sub.4 O).sub.7.7 C.sub.3 H.sub.6 Si(Me)O).sub.8 SiMe.sub.3

"Surfactant CC" denotes a blended composition consisting of

    ______________________________________                                        Component           Parts by Weight                                           ______________________________________                                        Siloxane Surfactant.sup.1                                                                         35                                                        Anionic Surfactant.sup.2                                                                          35                                                        Tall Oil            15                                                        Hexylene Glycol     15                                                        Ionol.sup.3         2500 ppm                                                  ______________________________________                                         .sup.1 A siloxane polymer having the average composition formula Me.sub.3     SiO(Me.sub.2 SiO).sub.5.1 [MeO(C.sub.2 H.sub.4 O).sub.7.2 C.sub.3 H.sub.6     Si(Me)O].sub.7.5 SiMe.sub.3                                                   .sup.2 An organic anionic surfactant which is a sodium sulfonate of a         petroleum hydrocarbon mixture a typical analysis of which is (wt. %) 62.0     sodium sulfonate; 32.7 mineral oil, 4.5 water; 0.7 inorganic salt; avg.       mol. wt. of sulfonate portion to 435; flash point, C. O. C. 400°       F.; available commercially as "Bryton 430".                                   .sup.3 Parts per million parts of the other four components.             

"Surfactant DD" denotes a siloxane polymer having the averagecomposition formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.5.1 [MeO(C.sub.2 H.sub.4 O).sub.7.2 C.sub.3 H.sub.6 Si(Me)O].sub.7.5 SiMe.sub.3

EXAMPLE 1

In a three neck round bottom flask fitted with a mechanical stirrer,nitrogen sparge tube, thermometer, addition funnel, reflux column andcold water bath, about 5 grams of a 20 weight percent aqueous solutionof NaOH (about 0.22 wt. % NaOH in the reaction mixture) were added toabout 400 grams of an allyl and hydroxyl end-blocked polyoxyalkylenehaving an average molecular weight of about 388 and an averagecomposition formula

    H.sub.2 C = CHCH.sub.2 O (C.sub.2 H.sub.4 O).sub.7.5 H

(wt. % OH about 4.36) covered by an atmosphere of nitrogen. About 53.1grams (about 100% of theory) of acrylonitrile (H₂ C = CHCH₂ CN) was thenfed to the mixture over a 2 hour period with constant stirring. Thetemperature of the mixture was maintained by occasional cooling at about25° C to 30° C. After this time the mixture was neutralized by theaddition of about 2 grams of 85 weight percent aqueous phosphoric acid(H₃ PO₄). The neutralized mixture was then mixed with Magnesol(magnesium silicate) and then filtered to give a clear off-colorlessproduct filtrate. The filtrate was desolvated by rotary evaporation at atemperature not exceeding about 100° C. under reduced pressure to aconstant weight. There was obtained about 498.5 grams of the desiredpolyether product having the average composition formula

    H.sub.2 C = CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.7.5 CH.sub.2 CH.sub.2 CN

analysis of the desired product showed about 0.8 weight % residualhydroxyl groups and that about 85 percent of the starting polyether wascyanoethylated.

EXAMPLE 2

In a manner similar to Example 1, the acrylonitrile-cappedpolyoxyalkylene composition product having the average formula

    H.sub.2 C = CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.7.9 CH.sub.2 CH.sub.2 CN

was prepared using about 400 grams of H₂ C = CHCH₂ O(C₂ H₄ O)hd 7.9 H(average mol. wt. about 406; wt. % OH about 4.36), about 0.5 grams ofIonol, about 2.5 grams of 20 wt. % aqueous NaOH (about 0.10 wt. % NaOHin the reaction mixture) and about 106.1 grams of acrylonitrile (about200% of theory). The reaction was conducted at about 15° C. to 25° C.over 11/4 hours. After an additional 12/3 hours the orange coloredproduct composition was neutralized with about 1.0 gram of 85 wt. %aqueous H₃ PO₄ and vacuum desolvated at 90° C/1.0 mm Hg. The neutralizedreaction product was then mixed with about 60 grams of Magnesol, dilutedwith toluene and pressure filtered. The filtrate was then desolvated byrotary evaporation. Analysis of the desired polyether product showedabout 0.03% residual hydroxyl groups and that about 99.3 percent of thestarting polyether was cyanoethylated.

EXAMPLE 3

In a manner similar to Example 2, the acrylonitrile-cappedpolyoxyalkylene composition product having the average formula

    H.sub.2 C = CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.7.9 CH.sub.2 CH.sub.2 CN

was again prepared using about 400 grams of H₂ C ═ CHCH₂ O(C₂ H₄ O)₇.9 H(avg. mol. wt. about 406; wt. % OH about 4.36), about 0.05 grams ofIonol, about 10 grams of 20 wt. % NaOH (about 0.04 wt. % NaOH in thereaction mixture), and about 58 grams of acrylonitrile (about 110% oftheory). The reaction was conducted at about 10° C to 13° C over 13/4hours. After about an additional hour the pale yellow colored productcomposition was neutralized with about 1.0 gram of 85 wt. % aqueous H₃PO₄ and the neutralized product mixture then rotary evaporated andstripped at 90° C/0.3 mm Hg. The desired polyether product developed adeep orange to reddish color and analysis showed about 0.27 wt. %residual hydroxyl group and that about 93.8 percent of the startingpolyether was cyanoethylated.

EXAMPLE 4

In a manner similar to Example 3, the acrylonitrile-cappedpolyoxyalkylene composition product having the average formula

    H.sub.2 C ═ CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.7.9 CH.sub.2 CH.sub.2 CN

was again prepared using about 400 grams of H₂ C ═ CHCH₂ O(C₂ H₄ O)₇.9 H(average mol. wt. about 406; wt. % OH about 4.36), about 0.05 grams ofIonol, about 1.0 grams of 20 wt. % aqueous NaOH (about 0.044 wt. % NaOHin the reaction mixture) and about 53 grams of acrylonitrile (about 100%of theory). The reaction was conducted at about 8° C to 10° C. over 1hour. After an additional hour the light yellow product composition wasneutralized with about 0.5 grams of 85 wt. % aqueous H₃ PO₄ and theneutralized mixture desolvated by rotary evaporation at 75° C/0.3 mm Hg.The product composition was then diluted with an equal amount oftoluene, pressure filtered and the filtrate desolvated by rotaryevaporation of 90° C/0.3 mm Hg. Analysis of the desired polyetherproduct showed about 0.35% residual hydroxyl groups, that about 92percent of the starting polyether was cyanoethylated and the product tohave a Brookfield viscosity (at room temperature) at about 43centipoises.

EXAMPLE 5

In a manner similar to Example 4, the acrylonitrile-cappedpolyoxyalkylene composition product having the average formula

    H.sub.2 C ═ CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.7.9 CH.sub.2 CH.sub.2 CN

was again prepared using about 992 grams of H₂ C ═ CHCH₂ O(C₂ H₄ O)₇.9 H(avg. mol. wt. about 406; wt. % OH about 4.36), about 2.5 grams of 20wt. % aqueous NaOH (about 0.045 wt. % NaOH in the reaction mixture), andabout 131.5 grams of acrylonitrile (about 97.6% of theory). The reactionwas conducted at about 3° C. to 5° C. over 3 hours. After an additionalhalf hour the product composition was neutralized with about 1.25 gramsof 85 wt. % aqueous H₃ PO₄. About 50 grams of toluene were added to theneutralized reaction mixture which was then desolvated by rotaryevaporation at 85° C/1.5 mm Hg. During this treatment the product turnedwine-red in color. About 40 grams of Magnesol was then added to theproduct which was then pressure filtered. The filtrate was wine-red incolor and analysis of the desired product showed about 0.34% residualhydroxyl groups, that about 92.2% of the starting polyether wascyanoethylated and the product to have a Brookfield viscosity (at roomtemperature) of about 37 centipoises.

EXAMPLE 6

In a manner similar to Example 5, the acrylonitrile-cappedpolyoxyalkylene composition product having the average formula

    H.sub.2 C ═ CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.7.9 CH.sub.2 CH.sub.2 CN

was again prepared using about 400 grams of H₂ C ═ CHCH₂ O(C₂ H₄ O)₇.9 H(avg. mol. wt. about 406; wt. % OH about 4.36), about 1.0 gram of 20 wt.% aqueous NaOH (about 0.044 wt. % NaOH in the reaction mixture), andabout 49.0 grams of acrylonitrile (about 92% of theory). The reactionwas conducted at about 3° C to 8° C over 23/4 hours. After an additionalhalf hour the light yellow colored product composition was neutralizedwith about 0.45 grams of 85 wt. % aqueous H₃ PO₄ and the neutralizedmixture desolvated by rotary evaporation at 95° C/0.5 mm Hg. About 40grams of Magnesol and about 400 grams of toluene were then added to theneutralized product which was then pressure filtered and the filtratedesolvated by rotary evaporation at 95° C/0.5 mm Hg. Analysis of thedesired polyether product which was light yellow-brown in color showedabout 0.5% residual hydroxyl groups, that about 88.7 percent of thestarting polyether was cyanoethylated and the product to have aBrookfield viscosity (at room temperature) of about 37 centipoises.

EXAMPLE 7

In a manner similar to Example 6, the acrylonitrile-cappedpolyoxyalkylene composition product having the average formula

    H.sub.2 C ═ CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.7.9 CH.sub.2 CH.sub.2 CN

was again prepared using about 1000 grams of

    H.sub.2 C ═ CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.7.9 H

(avg. mol. wt. about 406; wt. % OH about 4.36), about 3.0 grams of a 20weight percent aqueous solution of Me₄ NON (about 0.05 wt. % Me₄ NOH inthe reaction mixture), and about 143 grams of acrylonitrile (about 105%of theory). The reaction was conducted at about 10° C. to 18° C. over a1 hour period. Infrared analysis at this time showed the presence of aslight amount of unreacted hydroxyl moiety. Stirring was maintained foran additional one half hour at about 18° C. after which infraredanalysis indicated essentially a complete reaction. After this time themixture was neutralized by addition of about 3.05 grams of 85 weightpercent aqueous H₃ PO₄. About 50 grams of Magnesol were added to theneutralized mixture which was then pressure filtered. Then about 200grams of toluene were added to a 400 gram portion of the filtrate whichwas then desolvated by rotary evaporation at 90 ° C/< 0.5 mm Hg.Analysis of the desired polyether product thus obtained showed about0.185 wt. % residual hydroxyl groups, that about 95.8 percent of thestarting polyether was cyanoethylated and the product to have aBrookfield viscosity (at room temperature) of about 40 centipoises.

EXAMPLE 8

In a manner similar to Example 7, the acrylonitrile-cappedpolyoxyalkylene composition product having the average formula

    H.sub.2 C ═ CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.10 CH.sub.2 CH.sub.2 CN

was prepared using about 300 grams of H₂ C ═ CHCH₂ O(C₂ H₄ O)₁₀ H (avg.mol. wt. about 500; wt. % OH about 3.40) in about 200 grams of toluene,about 0.65 grams of 20 wt. % aqueous Me₄ NOH (about 0.023 wt. % Me₄ NOHin the reaction mixture) and about 33.2 grams of acrylonitrile (about110% of theory) in about 33.2 grams of toluene. The reaction wasconducted at about 7° C to 17° C for about 2 hours. After an additional11/2 hours the light brown colored product composition was neutralizedwith about 0.75 grams of 85 wt. % aqueous H₃ PO₄. About 30 grams ofMagnesol was added to the neutralized mixture which was then pressurefiltered. The filtrate was then desolvated by rotary evaporation at 90°C/< 1 mm Hg. Analysis of the desired polyether product which had ayellow color showed about 0.17 wt. % residual hydroxyl groups, thatabout 95 percent of the starting polyether was cyanoethylated and theproduct to have a Brookfield viscosity (at room temperature) of about 55centipoises.

EXAMPLE 9

In a manner similar to Example 8, the acrylonitrile-cappedpolyoxyalkylene composition product having the average formula

    H.sub.2 C ═ CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.9.5 (C.sub.3 H.sub.6 O).sub.0.8 CH.sub.2 CH.sub.2 CN

was prepared using about 483 grams of H₂ C ═ CHCH₂ O(C₂ H₄ O)₉.5 --(C₃H₆ O)₀.8 H (average mol. wt. about 501.5; wt. % HO about 3.39; theoxyethylene and oxypropylene groups being present in a random fashion)in about 100 grams of toluene, about 1.5 grams of 20 wt. % aqueous Me₄NOH (about 0.047 wt. % Me₄ NOH in the reaction mixture) and about 53.0grams of acrylonitrile (about 110% of theory). The reaction wasconducted at about 8° C to 18° C for about 23/4 hours. The light browncolored product composition was neutralized without 1.8 grams of 85 wt.% aqueous H₂ PO₄ and the product turned light-yellow in color. About 30grams of Magnesol was added to the neutralized mixture and the mixturepressure filtered. The filtrate was then desolvated by rotaryevaporation at 90° C/< 0.5 mm Hg. Analysis of the yellow colored desiredpolyether product showed about 0.25 wt. % residual hydroxyl groups andthat about 92.5 percent of the starting polyether was cyanoethylated.

EXAMPLE 10

In a manner similar to Example 9, the acrylonitrile-cappedpolyoxyalkylene composition product having the average formula

    CH.sub.2 ═ CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.21.2 (C.sub.3 H.sub.6 O).sub.5.35 CH.sub.2 CH.sub.2 CN

was prepared using about 300 grams of

    CH.sub.2 ═ CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.21.2 (C.sub.3 H.sub.6 O).sub.5.35 H

(avg. mol. wt. about 1250; wt. % OH about 1.36; the oxyethylene andoxypropylene groups being present in a random fashion) in about 200grams of toluene; about 1.0 grams of 20 wt. % aqueous Me₄ NOH (about0.04 wt. % Me₄ NOH in the reaction mixture) and about 15 grams ofacrylonitrile (about 92% of theory) in about 15 grams of toluene. Thereaction was conducted at about 15° C to 23° C for about 2 hours. Thereaction product was neutralized with about 1.05 grams of 85wt. %aqueous H₃ PO₄. About 15 grams of Magnesol was added to the neutralizedmixture and the mixture pressure filtered. The filtrate was thendesolvated by rotary evaporation at 90° C/< 0.5 mm Hg. Analysis of theyellow-light brown colored desired polyether product showed about 0.23wt. % residual hydroxyl groups, that about 83 percent of the startingpolyether was cyanoethylated and the product to have a Brookfieldviscosity (at room temperature) of about 220 centipoises.

EXAMPLE 11

In a three-necked reaction flask equipped with a mechanical stirrer,distilling take-off head and thermometer a mixture of about 30.0 gramsof a hydrosiloxane polymer having an average molecular weight of about952 and the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.5 (MeHSiO).sub.7 SiMe.sub.3

(Anal: Si--H, 165 cc H₂ /gram; Calc: 0.2211 mole MeHSiO) and about 104.7grams (0.2379 mole) of the acrylonitrile-capped polyoxyalkylene productof Example 1 having the average formula

    H.sub.2 C ═ CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.7.5 CH.sub.2 CH.sub.2 CN

(about 7.7% excess of theory), and about 50 ml. of xylene was heatedrapidly to 45° C. with constant stirring. At that temperature about 20parts per million of platinum as chloroplatinic acid was added to thesystem. There was an exothermal reaction noted. The reaction mixture wasmaintained at 85° C-95° C for 1 hour after which analysis of thereaction mixture for residual Si--H was negative, indicating that thereaction had gone to completion. The reaction mixture was then cooled,neutralized with NaHCO₃, filtered and the filtrate desolvated by rotaryevaporation at 50° C/5 mm Hg. The desired arylonitrile-cappedpolyoxyalkylene-polysiloxane product was a clear amber liquid having theaverage formula ##STR26## This siloxane product, designated herein asSurfactant A, had a Brookfield viscosity (at about 25° C) of 480centipoises and a GPC average molecular weight of 4,000.

EXAMPLE 12

In a manner similar to Example 11 a mixture of about 24.1 grams of ahydrosiloxane polymer having an average molecular weight of about 1012and the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.5 (MeHSiO).sub.8 SiMe.sub.3

(Anal: Si--H, 176.3 cc H₂ /gram; Calc: 0.1898 mole MeHSiO) and about119.5 grams of the acrylonitrile-capped polyoxyalkylene product ofExample 4 having the average formula

    H.sub.2 C ═ CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.7.9 CH.sub.2 CH.sub.2 CN

(about 37% excess of theory) and about 110 grams of toluene was heatedto about 79° C with stirring. The reaction mixture was then catalyzedwith about 25 parts per million of platinum as chloroplatinic acidcatalyst and the reaction conducted at 79° C to 115° C for 6 hours.Additional platinum catalyst, 20 ppm platinum after 10 minutes, andabout 25 ppm platinum after 3 hours, was added during the reaction.After said 6 hours the reaction mixture was analyzed for residual Si--Hand yielded 0.60 cc H₂ /4.0cc sample, indicating that the reaction hadgone to 99.0 percent completion. The reaction mixture was then cooled,neutralized with NaHCO₃ and filtered. The filtrate was then desolvatedby rotary evaporation at 95° C/<0.3 mm Hg. The desiredacrylonitrile-capped polyoxyalkylene-polysiloxane product was a clearbrown liquid having the average formula ##STR27## This siloxane product,designated herein as Surfactant B had a GPC average molecular weight ofabout 4,400.

EXAMPLE 13

In a manner similar to Example 12, a mixture of about 24.1 grams of ahydrosiloxane polymer having an average molecular weight of about 1012and the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.5 MeHSiO).sub.8 SiMe.sub.3

(Anal: Si--H, 176.3 ccH₂ /gram; Calc: 0.1898 mole MeHSiO) about 119.5grams of the acrylonitrile-capped polyoxyalkylene product of Example 6having the average formula

    H.sub.2 C ═ CHCH.sub.2 O(C.sub.2 H.sub.4l O).sub.7.9 CH.sub.2 CH.sub.2 CN

(about 37% excess of theory), and about 110 grams of toluene was heatedto about 81° C with stirring. The reaction mixture was then catalyzedwith about 25 parts per million of platinum as chloroplatinic acid andthe reaction conducted at 81° C to 100° C for 3 hours. Additionalplatinum catalyst, about 20 ppm platinum after 1/2 hour and about 15 ppmplatinum after 2 hours, was added during the reaction. After said 3hours, the reaction mixture was analyzed for residual Si--H and yielded0.2 cc H₂ /4cc sample, indicating that the reaction had gone to 99.7percent completion. The reaction mixture was then cooled, neutralizedwith NaHCO₃ filtered and the filtrate desolvated by rotary evaporationat 95° C/<0.3 mm Hg. The desired acrylonitrile-cappedpolyoxyalkylene-polysiloxane product was a clear light brown liquidhaving the average formula ##STR28## This siloxane product, designatedherein as Surfactant C, had a Brookfield viscosity (at room temperature)of about 300 centipoises and a GPC average molecular weight of about4500.

EXAMPLE 14

In a similar manner to Example 13, a mixture of about 25.4 grams of ahydrosiloxane polymer having an average molecular weight of about 1012and the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.5 (MeHSiO).sub.8 SiMe.sub.3

(Anal: Si--H 176.3 cc H₂ /gram; Calc: 0.20 mole MeHSiO), about 161 gramsof the acrylonitrile-capped polyoxyalkylene product of Example 8 havingthe average formula

    H.sub.2 C ═ CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.10 CH.sub.2 CH.sub.2 CN

(about 40% excess of theory), and about 186.4 grams of toluene washeated to about 82° C with stirring. The reaction mixture was thencatalyzed with about 25 parts per million platinum as chloroplatinicacid and the reaction conducted at 82° C to 98° C for 31/2 hours.Additional platinum catalyst, about 20 ppm platinum after 20 minutes,about 20 ppm platinum after 11/2 hours and about 25 ppm platinum about 3hours was added during the reaction. After said 31/2 hours the reactionmixture was analyzed for residual Si--H and yielded 0.60 cc H₂ /5.0cc.sample indicating that the reaction had gone to 99 percent completion.The reaction product was cooled to room temperature, neutralized withNaHCO₃ and filtered. The filtrate was then desolvated by rotaryevaporation at 95° C/< 0.5 mm Hg. The desired acrylonitrile-cappedpolyoxyalkylene-polysiloxane product was a clear brown liquid having theaverage formula ##STR29## This siloxane product, designated herein asSurfactant D, had a Brookfield viscoity (at room temperature) of about500 centipoises and a GPC average molecular weight of about 7500.

EXAMPLE 15

In a similar manner to Example 14, a mixture of about 31.75 grams of ahydrosiloxane polymer having an average molecular weight of about 1012and the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.5 (MeHSiO).sub.8 SiMe.sub.3

(Anal: Si--H, 176.3 cc. H₂ /gram; Calc: 0.2501 mole MeHSiO), about143.75 grams of the acrylonitrile-capped polyoxyalkylene product ofExample 7 having the average formula

    H.sub.2 C ═ CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.7.9 CH.sub.2 CH.sub.2 CN

(about 25% excess of theory) and about 175.5 grams of toluene was heatedto about 90° C with stirring. The reaction mixture is then catalyzedwith about 20 parts per million of platinum as chloroplatinic acidcatalyst and the reaction conducted at 90° C to 110° C for 21/2 hours.Additional platinum catalyst, about 20 ppm platinum after 1/4 hour,about 10 ppm platinum after 1/2 hour and about 10 ppm platinum after 1hour was added during the reaction. After said 21/2 hours the reactionmixture was analyzed for residual Si--H and yielded 1.0 ccH₂ /4.0cc,sample, indicating that the reaction had gone to 98.5 percentcompletion. The reaction product was cooled to room temperature,neutralized with NaHCO₃ and filtered. The filtrate was then desolvatedby rotary evaporation at 90° C/< 0.5 mm Hg. The desiredacrylonitrile-capped polyoxyalkylene-polysiloxane product was a cleardark brown liquid having the average formula ##STR30## This siloxaneproduct designated herein as Surfactant E, had a Brookfield viscosity(at room temperature) of about 496 centipoises and a GPC averagemolecular weight of about 4700.

EXAMPLE 16

In a similar manner to Example 15, a mixture of about 35.0 grams of ahydrosiloxane polymer having an average molecular weight of about 892and the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.5 (MeHSiO).sub.6 SiMe.sub.3

(Anal: SiH, 153.6 ccH₂ /gram; Calc: 0.240 mole MeHSiO), about 138.0grams (0.3 mole) of the acrylonitrile-capped polyoxyalkyene product ofExample 7 having the average formula

    H.sub.2 C ═ CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.7.9 CH.sub.2 CH.sub.2 CN

(about 25% excess of theory) and about 173.0 grams of toluene was heatedto about 90° C with stirring. The reaction mixture was then catalyzedwith about 30 parts per million of platinum as chloroplatinic acidcatalyst and the reaction conducted at 90° C to 109° C for 11/2 hours.The reaction mixture was then analyzed for residual Si--H and yielded0.75 cc H₂ /4.0 cc sample, indicating that the reaction had gone to 98.8percent completion. The reaction product was cooled to room temperature,neutralized with NaHCO₃ and filtered. The filtrate was then desolvatedby rotary evaporation at 90° C/<0.5 mm Hg. The desiredacrylonitrile-capped polyoxyalkylene-polysiloxane product was a clearbrown liquid having the average formula ##STR31## The siloxane product,designted herein as Surfactant F, had a Brookfield viscosity (at roomtemperature) of about 335 and a GPC average molecular weight of about3900.

EXAMPLE 17

In a manner similar to Example 16, a mixture of about 27.9 grams of ahydrosiloxane polymer having an average molecular weight of about 1,132and the average formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.5 (MeHSiO).sub.10 SiMe.sub.3

(Anal: Si--H, 205.0 cc H₂ /gram; Calc; 0.2555 mole MeHSiO), about 146.6grams of the acrylonitrile-capped polyoxyalkylene product of Example 7having the average formula

    H.sub.2 C ═CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.7.9 CH.sub.2 CH.sub.2 CN

(about 25% excess of theory) and about 174.5 grams of toluene was heatedto about 90° C with stirring. The reaction mixture was then catalyzedwith about 30 parts per million of platinum as chloroplatinic acidcatalyst and the reaction conducted at 90° C to 109° C. for 31/2 hours.Additional platinum catalyst, about 10 ppm platinum after 1/6 hour andabout 10 ppm platinum after 1 hour was added during the reaction. Aftersaid 31/3 hours the reaction mixture was analyzed for residual Si--H andyielded 0.75 cc H₂ /4.0 cc sample, indicating that the reaction had goneto 98.9 percent completion. The reaction product was cooled, neutralizedwith NaHCO₃ and filtered. The filtrate was then desolvated by rotaryevaporation at 90° C/< 0.5 mm Hg. The desired acrylonitrile-cappedpolyoxyalkylene-polysiloxane product was a clear light brown liquidhaving the average formula ##STR32## This siloxane product, designatedherein as Surfactant G, had a Brookfield viscosity (at room temperature)of about 478 and a GPC average molecular weight of about 4700.

EXAMPLE 18

In a manner similar to Example 11, a mixture of about 10.4 grams of ahydrosiloxane polymer having an average molecular weight of about 416and the average formula

    Me.sub.3 SiO(Me.sub.2 SiO)(MeHSiO).sub.3 SiMe.sub.3

(Anal: Si--H, 161.3 cc H₂)gram; Calc: 0.07498 mole MeHSiO) and about42.2 grams of the acrylonitrile-capped polyoxyalkylene product ofExample 1 having the average formula

    H.sub.2 C ═ CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.7.5 CH.sub.2 CH.sub.2 CN

(about 28% excess of theory) and about 30 ml. of xylene was heated at45° C with constant stirring. At that temperature about 50 parts permillion of platinum as chloroplatinic acid catalyst was added to thesystem. There was an exothermal reaction noted. The reaction mixture wasmaintained at 85° C-95° C for 1 hour until completed. The reactionmixture was then cooled, neutralized with NaHCO₃, filtered and thefiltrate desolvated by rotary evaporation at 50° C/5 mm Hg. about 50.1grams of the desired acrylonitrile-capped polyoxyalkylene-polysiloxaneproduct having the average formula ##STR33## was obtained. Said siloxaneproduct is designated herein as Surfactant H.

EXAMPLES 19-32

In these examples, flexible polyester polyurethane foam containing aflame-retarding agent were produced using the above-describedSurfactants A through H of this invention (and with the above-describedControl Surfactants AA, BB and CC, not of this invention) as therespective foam stabilizing surfactant component of the foam-producingreaction mixture, designated herein as Foam Formulation A, which has thecomposition given in Table I, which follows.

                  TABLE I                                                         ______________________________________                                        FOAM FORMULATION A                                                            Component           Parts by Weight                                           ______________________________________                                        Surfactant          Varied (0.5 to 1)                                         Polyester Polyol.sup.1                                                                            100.0                                                     N-ethylmorpholine   1.9                                                       Hexadecyldimethylamine                                                                            0.3                                                       Water               3.6                                                       Tolylene diisocyanate                                                                             45.2                                                      (Index 105).sup.2                                                             Tris(2-chloroethyl)phosphate                                                                      7.0                                                       ______________________________________                                         .sup.1 The polyester polyol employed was a commercially available             polyester resin produced from adipic acid, diethylene glycol and              trimethylol propane in a mole ratio of approximately 1:1:0.2. This            polyester has a hydroxyl number of about 50 to 56, a molecular weight of      about 2,000, an acid number not greater than 2 and a viscosity of about       17,000 centistokes at about 25° C. This particular polyester is        known as "Witco Fomrez No. 50" (Witco Chemical Corporation).                  .sup.2 This component was a mixture of 2,4-tolylene diisocyanate (80          weight percent) and 2,6-tolylene diisocyanate. Index 105 means that the       amount of mixture employed was 105 percent of the stoichiometric amount       required to react with the polyester polyol and water present in the foam     formulation.                                                             

The runs of Examples 19-32 were carried out in accordance withsubstantially the same general procedure which entailed the followingsteps. The surfactant, amine catalysts and water were premixed in a 50milliliter beaker. The polyester polyol reactant was weighted into atared 32-ounce capacity container. The flame-retardant[tris(2-chloroethyl)phosphate] and tolylene diisocyanate reactant werealso weighed into the container and mixed with a spatula untilhomogeneous. Further mixing was done on a drill press equipped with adouble three-bladed marine-type propeller about 3 inches in diameter.The mixing in the drill press was accomplished at 1000 revolutions perminute for 8 seconds. Then the premixture of surfactant, catalyst andwater was added and mixing was continued for 7 additional seconds. Thereaction mixture was poured into a 12 in. × 12 in. × 12 in. cardboardbox, was allowed to rise and was then cured for about 30 minutes at 130°C. Samples of the foam products prepared for breathability and for adetermination of burning resistance (burning extent and flame rating) inaccordance with ASTM D-1962-68 and the results are given in Table IIwhich follows:

                                      TABLE II                                    __________________________________________________________________________                    FOAM QUALITY             FLAMMABILITY                         Example    Parts by                                                                           Rise                                                                              Breathability                                                                         Top Collapse                                                                          Density                                                                            Burning  Rat-                        Number                                                                             Surfactant                                                                          Weight                                                                             Inches                                                                            SCFM    (Inches)                                                                              lb/ft..sup.3                                                                       Extent(Inches)                                                                         ing                         __________________________________________________________________________    19   A     1    5.5 0.7     0.3     2.21 2.6      SE                          20   A     0.5  5.2 1.4     None    2.11 1.6      SE                          21   B     1.0  --   1.15   0.1     2.08 2.0      SE                          22   C     1.0  5.2 1.2     0.3     2.15 2.0      SE                          23   C     0.5  5.3 2.6     0.1     2.21 1.6      SE                          24   D     0.5  5.2 TIGHT   --      --   1.9      SE                          25   E     0.5  5.8 4.3     NONE    2.2  1.8      SE                          26   F     0.5  5.2 6.0     0.2     1.96 3.4      SE                          27   G     0.5  5.1 1.0     NONE    2.16 1.7      SE                          28   H     1.0  5.4 1.4     NONE    --   1.7      SE                          29   H     0.5  5.4 TIGHT   --      --   --       --                          30   AA+   1.0  5.6 2.0     NONE    2.01 2.2      SE                          31   BB+   0.5  5.0 5.8     0.4     2.03 2.7      SE                          32   CC+   1.0  --   1.15   SLIGHT  2.03 5        B                           __________________________________________________________________________     AA+, BB+, CC+ - Surfactants not of this invention                        

The data in Table II above demonstrates that the acrylonitrile-cappedpolyoxyalkylene-polysiloxane surfactant polymers of this invention areeffective stabilizers of flexible polyester foam and possess the furtherdesirable property of allowing for the formation of flexible polyesterfoam containing a flame retardant which foam has a self-extinguishingflammability rating as tested above.

EXAMPLES 33-36

In accordance with these examples, a repeated preparative example ofSurfactant E, herein designated Surfactant E', was blended with variousorganic compounds to provide illustrative solution compositions of thisinvention. These blended compositions are designated herein as BlendedSurfactants I through L and each was used as the surfactant component ofFoam Formulation A above in a concentration of one part by weight,following the general procedure described above with reference toExamples 19-32. In using the blended surfactants, clear, homogeneousaqueous premixtures were obtained when the water and amine catalysts ofFoam Formulation A were combined therewith. The composition of theblended surfactants and the results of these examples are given in thefollowing Table III.

                                      TABLE III                                   __________________________________________________________________________    SURFACTANT COMPOSITION                                                        Example                                                                            Blended       Wt. % of                                                                             Breathability                                                                        Density                                                                            Burning Flamability                     Number                                                                             Surfactant                                                                         Components                                                                             Components                                                                           SCMF   Lb/Ft.sup.3                                                                        Extent (Inches)                                                                       Rating                          __________________________________________________________________________    33   I    Surfactant E'                                                                          35     0.8    2.18 1.9     SE                                        Nonionic .sup.1                                                                        28                                                                   Tall Oil 20                                                                   Hexylene Glycol                                                                        15                                                                   Water     2                                                         34   J    Surfactant E'                                                                          50     3.0    2.06 3.23    SE                                        Nonionic .sup.1                                                                         8                                                                   Tall Oil 20                                                                   Hexylene Glycol                                                                        20                                                                   Water     2                                                         35   K    Surfactant E'                                                                          50     2.9    2.09 2.9     SE                                        Nonionic .sup.1                                                                        13                                                                   Tall Oil 20                                                                   Hexylene Glycol                                                                        15                                                                   Water     2                                                         36   L    Surfactant E'                                                                          35     2.5    2.06  2.38   SE                                        Anionic .sup.2                                                                         35                                                                   Tall Oil 20                                                                   Hexylene Glycol                                                                        10                                                         __________________________________________________________________________     .sup.1 An organic nonionic surfactant in which the hydrophobe is a mixtur     of C.sub.11 -C.sub.15 alcohols and the hydrophile is ethylene oxide (avg.     9 mols/mol of hydrophobe).                                                    .sup.2 An organic anionic surfactant which is a sodium sulfonate of a         petroleum mixture and which is the same as defined in Surfactant CC above                                                                              

The data in Table III demonstrates that solution compositions of thearylonitrile-capped polyoxyalkylene-polysiloxane polymers of thisinvention in addition to forming clear homogeneous premixtures withwater and amine catalysts, also possess good potency as effectivestabilizers of flexible foam and further possess the desirable propertyof allowing for the formation of said foam containing a flame-retardantwhich foam has a self-extinquishing flammability rating as tested above.

EXAMPLES 37-40

In these examples a potency determination was made of above-describedSurfactants A and C of this invention (and above-described ControlSurfactants AA and DD, not of this invention) as the foam stabilizingsurfactant in the production of flexible polyester polyurethane foamusing Foam Formulation B as identified in Table IV, which follows:

                  TABLE IV                                                        ______________________________________                                        FOAM FORMULATION B                                                            Component           Parts by Weight                                           ______________________________________                                        Surfactant (varied) Varied (0.5 to 1)                                         Polyester Polyol.sup.1                                                                            100                                                       N-ethylmorpholine   1.9                                                       Hexadecyldimethylamine                                                                            0.3                                                       Water               5.0                                                       Tolylene Diisocyanate                                                                             59.4                                                      (Index 105).sup.2                                                             ______________________________________                                         .sup.1 As identified in footnote .sup.1 of Table I                            .sup.2 As indicated in footnote .sup.2 of Table I                        

As indicated, Foam Formulation B contains 5 parts by weight of water per100 l parts by weight of polyol reactant. The 5 parts water system isusually more difficult to stabilize than the more conventionalformulations containing less water and thus provides a relativelysensitive test of potency. The foams were prepared following theabove-described foaming procedure except that no flame-retardant wasused. The results are given in Table V which follows.

                  TABLE V                                                         ______________________________________                                                         Parts                                                        Example          by      Rise  Cells   Cell                                   Number Surfactant                                                                              Weight  Inches                                                                              per Inch                                                                              Structure                              ______________________________________                                        37     A         0.5     8.2    10-15  COARSE                                 38     C         0.5     8.1    10-15  COARSE                                 39     AA+       1.0     8.1    10     COARSE                                 40     DD+       0.5     7.9    10     COARSE                                 ______________________________________                                         AA+ and DD+ - Surfactants not of this invention                          

The data of Table V demonstrates that the acrylonitrile-cappedpolyoxyalkylene-polysiloxane surfactants of this invention haveexcellent potency as reflected by the rise values of the flexiblepolyester foam products which do not contain a flame-retardant.

EXAMPLES 41 -43

In accordance with these examples, 3-cyanopropyl-substitutedpolymethylpolysiloxane hydride fluids, designated in the examples asSi--H Internediate Fluids I-III were prepared having the averagecomposition formula ##STR34## wherein the particular values of x, y andz are given in Table VI below. The respective fluids were prepared bythe acid-catalyzed equilibration of reactants (1)-(4) listed belowemploying trifluoromethylsulfonic acid.

Reactant (1): Hexamethyldisiloxane, Me₃ SiOSiMe₃, as the source of theendblocking trimethylsiloxy units, Me₃ SiO_(1/2) --.

Reactant (2): Cyclic polymers of dimethylsiloxane distilled to providethe cyclic tetramer, [Me₂ SiO]₄, as the predominant component (boilingpoint, 175° C./760 mm Hg.), as the source of the dimethylsiloxy units.

Reactant (3): Cyclic 3-cyanopropylmethylsiloxane polymer, as the sourceof the 3-cyanopropylmethylsiloxy units. This reaction is prepared by thehydrolysis of 3-cyanopropylmethyldichlorosilane, MeSiCl₂ (CH₂)₃ CN, at atemperature of about 10°-15° C. and subatmospheric pressure (40-110 mm.)employing toluene diluent and neutralizing the hydrolyzate with sodiumbicarbonate, followed by dehydration and cyclization of the hydrolyzatein the presence of sodium bicarbonate at reflux temperature, and removalof toluene from the cyclizate.

Reactant (4): Polymeric methylhydrogensiloxane (Si--H analysis, 355-365cc. H₂ per gram), as the source of the methylhydrogensiloxy) units.

The respective amounts of the aforesaid reactants (1)-(4) and catalystemployed in providing an analytical data pertaining to the respectivereaction products are given in Table VI; the procedure and reactionconditions employed are as typically illustrated by the followingdetailed description of the preparation of Intermediate Fluid I.

Preparation of Intermediate Fluid I

The aforesaid Reactants (1)-(4) were charged in the following amounts toa 500 ml. capacity, three-necked flask equipped with a thermometer,mechanical, stirrer, condenser and nitrogen blow-by:

Reactant (1): 16.2 grams, corresponding to 0.1 mole of Me₃ SiOSiMe₃ or0.2 mole-equivalents of Me₃ SiO_(1/2) ;

Reactant (2): 44.5 grams, corresponding to 0.6 mole-equivalent (x') ofthe unit, Me₂ SiO_(2/2) ;

Reactant (3): 101.78 grams, corresponding to 0.8 mole-equivalent (z') ofthe unit, NC(CH₂)₃ Si(Me)O_(2/2) ; and

Reactant (4): 36.0 grams, corresponding to 0.6 mole-equivalent (y') ofthe unit, MeHSiO_(2/2).

Also added was 0.8 gram of anhydrous trifluoromethyl sulfonic acidcatalyst corresponding to about 0.4 weight percent of the total weightof reactants. The heterogeneous reaction mixture was stirred at roomtemperature overnight (about 18 hours). The clear liquid equilibrate wasneutralized with sodium bicarbonate while stirring for about 1 hour, andfiltered. The liquid product had a viscosity of 116 centipoise. Basedupon the method and proportions of reactants employed expressed on thenormalized basis of two moles of M units, the fluid product, designatedSi--H Intermediate Fluid I, has the average composition: ##STR35##corresponding to a theoretical MeHSiO content of 18.1 weight percent.Upon Si--H analysis, the product provided 64.0 cc. H₂ /gram on the basisof which the found MeHSiO content is 17.4 weight percent.

As used herein, the weight percentages expressed as "% MeHSiO, Found"are derived from the Si--H Analysis (cc. H₂ per gram) in accordance withthe conversion:

    Weight Percent MeHSiO Found = cc H.sub.2 per gram × 100/373.3

where the factor 373.3 is the theoretical number of cubic centimeters ofhydrogen provided per gram of fluid consisting of 100 percent MeHSiO(that is, 22,400 cc. of hydrogen divided by the unit molecular weight of60). The weight percentages expressed as "%MeHSiO, Theoretical"correspond to the weight (60 y) contributed by MeHSiO divided by thecalculated molecular weight of the fluid product times 100.

The above data pertaining to Si--H Intermediate Fluid I, as well ascorresponding data for Si--H Fluids II and III are given in Table VIwhich follows.

                                      TABLE VI                                    __________________________________________________________________________    Preparation of Si-H Intermediate Fluids, where the average values             of x, y and z are given below.                                                EXAMPLE NUMBER     41    42   43                                              Si-H Intermediate Fluid                                                                          I     II   III                                             REACTANTS                                                                     Me.sub.3 SiOSiMe.sub.3 :                                                                 grams   16.2  16.2 16.2                                            moles /1/  0.1     0.1   0.1                                                  Me.sub.2 SiO.sub.2/2 :                                                                   grams /2/                                                                             44.5  44.5 74.15                                                      mole-eq. (x')                                                                         0.6   0.6  1.0                                             (CH.sub.2).sub.3 Si(Me)O.sub.2/2 :                                                       grams /3/                                                                             101.7 50.9 50.9                                                       mole-eq. (z')                                                                         0.8   0.4  0.4                                             Me(H)SiO.sub.2/2 :                                                                       grams /4/                                                                             36    36   36                                                         mole-eq. (y')                                                                         0.6   0.6  0.6                                             CATALYST                                                                      CF.sub.3 SO.sub.3 H, wt. %                                                                       0.4   0.8  0.4                                             Si-H Fluid Product                                                            Moles of Units /2Me.sub.3 SiO.sub.1/2                                         x (average)        6     6    10                                              z (average)        8     4    4                                               y (average)        6     6    6                                               Si-H Analysis                                                                 cc. H/gram         64.0  84.0 74.4                                            % Me(H)SiO :                                                                             Found /5/                                                                             17.4  22.5 19.9                                                       Theo.   18.1  24.4 20.3                                            Viscosity, centipoise                                                                            116        55                                              __________________________________________________________________________     /1/ Corresponding to 0.2 moles (or mole-equivalents) of Me.sub.3              SiO.sub.1/2.                                                                  /2/ Grams used of Reactant (2), corresponding to the indicated                mole-equivalents of the unit, Me.sub.2 SiO.sub.2/2.                           /3/ Grams used of Reactant (3), corresponding to the indicated                mole-equivalents of the unit NC/CH.sub.2).sub.3 Si(Me)O.sub.2/2.              4/4 Grams used of Reactant (4), corresponding to the indicated                mole-equivalents of the uint Me(H)SiO.sub.2/2.                                /5/ Corresponding to the cc. Hg/gram found.                              

EXAMPLE 44

In a manner similar to Example 8, the acrylonitrile-cappedpolyoxyalkylene composition product having the average formula

    H.sub.2 C ═ CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.7.5 CH.sub.2 CH.sub.2 CN

was prepared using about 4000 grams of H₂ C ═ CHCH₂ O(C₂ H₄ O)₇.5 H;about 800 grams of toluene; about 24 grams of 10 wt. % aqueous Me₄ NOHand about 572 grams of acrylonitrile. The reaction was conducted byadding the acrylonitrile dropwise to the reaction mixture over 40minutes while the reaction temperature was maintained with an ice bathat about 18° C. After all of the acrylonitrile had been added and theexothermic reaction completed the reaction mixture was then warmed toroom temperature and allowed to sit for 2 hours and then was neutralizedwith about 12 grams of 85 wt. % aqueous H₃ PO₄, About 200 grams ofMagnesol was added to the neutralized mixture and the mixture allowed tostand over night. The reaction mixture was then filtered and thefiltrate desolvated. Analysis of the desired polyether product showedaout 0.27 wt. % residual hydroxyl groups and that about 93 percent ofthe starting polyether was cyanoethylated.

EXAMPLE 45

Into a 500 ml., 3-necked flask equipped with a mechanical stirrer,thermometer and N₂ cover was charged about 39.7 grams (0.12 mole) of thehydrosiloxane polymer product of Example 41 having the average formula##STR36## (Si--H Intermediate Fluid I), about 70.8 grams (0.156 mole) ofthe acrylonitrile-capped polyoxyalkylene product of Example 44 havingthe average formula

    H.sub.2 C ═ CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.7.5 CH.sub.2 CH.sub.2 CN

(about 30% excess of theory); and about 100 ml. of toluene. The reactionmixture was heated to about 85° C. at which time 50 parts per million ofplatinum as chloroplatinic acid catalyst (about 0.0005 gram) was added.The reaction exothermed to 103° C. and was stirred over night as itcooled to room temperature. The reaction mixture was analyzed forresidual Si--H and yielded 0.0 cc H₂ /2 ml. aliquot, indicating that thereaction had gone to completion. The reaction mixture was thenneutralized by adding about 2 grams of NaHCO₃ and 1 gram of ATTACOTE andstirring for 1 hour. The neutralized reaction mixture was then filteredand the filtrate desolvated by rotary evaporation at 50° C/1 mm Hg. Thedesired acrylonitrile-capped polyoxyalkylene-polysiloxane product was aliquid having the average formula ##STR37## The siloxane product,designated herein as Surfactant M, had a Brookfield viscosity (at roomtemperatue) of about 400 centipoises and a GPC average molecular weightof about 4,600.

EXAMPLE 46

Into a 500 ml., 3-necked flask equipped with a mechanical stirrer,thermometer and N₂ cover was charged about 29.5 grams (0.12 mole) of thehydrosiloxane polymer product of Example 42 having the average formula##STR38## (Si--H Intermediate Fluid II); about 70.8 grams (0.156 mole)of the acrylonitrile-capped polyoxyalkylene product of Example 44 havingthe average formula

    H.sub.2 C = CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.7.5 CH.sub.2 CH.sub.2 CH.sub.2 CN

(about 30% excess of theory); and about 100 ml. of toluene. The reactionmixture was heated to about 85° C at which time 50 parts per million ofplatinum as chloroplatinic acid catalyst (about 0.0005 gram) was added.The reaction exothermed to 100° C. and was stirred overnight as itcooled to room temperature. Analysis of the reaction mixture indicatedthat the reaction had gone to completion. The reaction mixture was thenneutralized by adding about 2 grams of NaHCO₃ and 1 gram of ATTACOTE andstirring for 1 hour. The neutralized reaction mixture was then filteredand the filtrate desolvated by rotary evaporation at 50° C/1 mm Hg. Thedesired acrylonitrile-capped polyoxyalkylene-polysiloxane product was aliquid having the average formula ##STR39## The siloxane product,designated herein as Surfactant N, had a Brookfield viscosity (at roomtemperature) of about 175 centipoises and a GPC average molecular weightof about 3,300.

EXAMPLE 47

Into a 500 ml., 3-necked flask equipped with a mechanical stirrer,thermometer and N₂ cover was charged about 35.4 grams (0.12 mole) of thehydrosiloxane polymer product of Example 43 having the average formula##STR40## (Si--H Intermediate Fluid III), about 70.8 grams (0.156 mole)of the acrylonitrile-capped polyoxyalkylene product of Example 44 havingthe average formula

    H.sub.2 C = CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.7.5 CH.sub.2 CH.sub.2 CH.sub.2 CN

(about 30% excess of theory); and about 105 ml. of toluene. The reactionmixture was heated to about 85° C at which time 50 parts per million ofplatinum as chloroplatinic acid catalyst (about 0.0005 gram) was added.The reaction exothermed and was stirred over night as it cooled to roomtemperature. Analysis of the reaction mixture indicated that thereaction had gone to completion. The reaction mixture was thenneutralized by adding about 2 grams of NaHCO₃ and 1 gram of ATTACOTE andstirring for 1 hour. The neutralized reaction mixture was then filteredand the filtrate desolvated by rotary evaporation at 50° C/5mm Hg. Thedesired acrylonitrile-capped polyoxyalkylene-polysiloxane product was aliquid having the average formula ##STR41## The siloxane product,designated herein as Surfactant 0, had a Brookfield viscosity (at roomtemperature) of about 505 centipoises and a GPC average molecular weightof about 5,200.

EXAMPLES 48--51

In these examples, flexible polyester polyurethane foam containing aflame retardant were produced using the above described Surfactants Mthrough O of this invention (and the above described Control SurfactantAA) as the respective foam stabilizing surfactant component of thefoam-producing reacton mixture. Said foam-producing reaction mixture wasthe same as Foam Formulation A described above and the foams wereprepared and samples analyzed following the above described procedures.The results are given in Table VII which follows.

                                      TABLE VII                                   __________________________________________________________________________                    Foam Quality           Flamability                            Example    Parts by                                                                           Rise                                                                              Breathability                                                                         Cells per                                                                           Density                                                                            Burning                                Number                                                                             Surfactant                                                                          Weight                                                                             Inches                                                                            SCFM    Inch  Lb/ft.sup.3                                                                        Extent                                                                             Rating                            __________________________________________________________________________    48     M   0.35 5.4 1.0     45/50 2.10 1.6  28.3                              49   N     0.35 5.3 0.28    45/50 2.14 1.9  34.3                              50   O     0.35 5.5 1.9     45/50 2.08 2.7  58.0                              51   AA+   1.0  6.5 1.6     55/60 1.85 3.5  79                                __________________________________________________________________________     AA+ - Surfactant not of this invention                                   

The data in Table VII above demonstrates that the acrylonitrile-cappedpolyoxyalkylene-polysiloxane polymers of this invention are effectivestabilizers for flexible polyester polyurethane foam that contain aflame-retardant.

EXAMPLES 52-54

In these examples, flexible polyester polyurethane foam, not containinga flame-retardant, were produced using the above described Surfactants Mand N of this invention (and the above described Control Surfactant AA)as the respective foam stabilizing surfactant component of thefoam-producing reaction mixture. Said foam-producing reaction mixturewas the same as Foam Formulation B described above and the foams wereprepared and samples analyzed following the above described proceduresexcept no flame-retardant was used. The results are given in Table VIIIwhich follows:

                                      TABLE VIII                                  __________________________________________________________________________                    Foam Quality                                                  Example    Parts by                                                                           Rise                                                                              Breathability                                                                         Cells per                                         Number                                                                             Surfactant                                                                          Weight                                                                             Inches                                                                            SCFM    Inch  Density Lb./ft.                             __________________________________________________________________________    52    M    0.35 8.3 0.5     30/35 1.47                                        53    N    0.35 8.4 1.9     30/35 1.47                                        54    AA+  1.0  8.5 2.5     40/45 1.47                                        __________________________________________________________________________     AA+ - Surfactant not of this invention                                   

The data in Table VIII above demonstrates that the acrylonitrile-cappedpolyoxyalkylene-polysiloxane polymers of this invention are effectivestabilizers for flexible polyester polyurethane foam that does notcontain a flame-retardant.

EXAMPLE 55

An acrylonitrile-capped polyoxyalkylene composition was prepared in asimilar manner as described above by reacting a mixture of about 350lbs. of a polyether having an average molecular weight of about 390(allyl analysis) and the average composition formula H₂ C═CHCH₂ O(C₂ H₄O)₇.5 H and about 52.2 lbs. of acrylonitrile (5% excess of theory) alongwith about 135 grams of 10% aqueous H₃ PO₄. The reaction was conductedat 26° C to 32° C over 31/2 hours. Then about 20 lbs. of benzene wasadded, the reaction mixture vacuum stripped at about 75° C./62 mm Hg.and filtered to yield the desired allyl and acrylonitrile endblockedpolyether having the average composition formula

    H.sub.2 C═CHCH.sub.2 O(C.sub.2 H.sub.4 O).sub.7.5 CH.sub.2 CH.sub.2 CN

(anal. 9.04% allyl).

An acrylonitrile-polysiloxane polymer was then prepared in a similarmanner as described above using about 197 lbs. of the above allyl andarylonitrile endblocked polyether product, about 30 lbs. of isopropanol,about 14 gal. of toluene, about 40 lbs. of a hydrosiloxane polymerhaving the average composition formula

    Me.sub.3 SiO(Me.sub.2 SiO).sub.5.2 (MeHSiO).sub.7.6 SiMe.sub.3

(Anal. Si--H, 178 ccH₂ /gr.; Visc. 7.1 centistoke) and about 84 ml. ofchloroplatinic acid catalyst (10% ethanol-1,2 dimethoxy-ethanesolution). The reaction was conducted at about 95° C to 104° C for about12 hours after which analysis of the reaction mixture for residual Si--Hshowed 1.4 ccH₂ /gr. The reaction mixture was then sparged with ethylenefor 1 hour and analysis yielded only a trace of Si--H indicating thereaction was essentially completed. The reaction mixture was then vacuumstripped at about 29° C./80-120 mm Hg. to remove the toluene andisopropanol, cooled and filtered. The desired acrylonitrile-cappedpolyoxyalkylene-polysiloxane product was an amber liquid having theaverage composition formula ##STR42## This siloxane product, designatedherein as Surfactant P, had a Brookfield viscosity (at 25° C) of about372 and a specific gravity of 1.089. Analysis also showed 6.4%CN, 2%allyl and 0.53% OH.

EXAMPLES 56-57

In accordance with these examples above described Surfactant P wasblended with various organic compounds to provide illustrative solutioncompositions of this invention. These blended compositions aredesignated herein as Blended Surfactants Q and R. The solutioncomposition of said blended surfactants is given in Table IX which is asfollows:

                  TABLE IX                                                        ______________________________________                                        Example  Blended                 Wt. % of                                     Number   Surfactant Components   Components*                                  ______________________________________                                        56       Q          Surfacatnt P 35                                                               Anionic/1/   35                                                               Tall Oil     15                                                               Hexylene                                                                      Glycol       15                                           57       R          Surfacant P  52                                                               Nonionic/2/    10.4                                                           Tall Oil       15.6                                                           Hexylene                                                                      Glycol       21                                           ______________________________________                                         *Ionol was also present in Blended Surfactants Q (10000 ppm) and R (1%).      /1/An organic anionic surfactant which is a sodium sulfonate of a             hydrocarbon mixture available commercially as "Petronate L" (Witco            Chemical Company).                                                            /2/An organic nonionic surfactant in which the hydrophope is a mixture of     C.sub.11 to C.sub.15 alcohols and the hydrophile is ethylene oxide (avg.      mols/mol of hydrophobe).                                                 

EXAMPLES 58 - 67

In accordance with these examples, a series of machine scale flexiblepolyester urethane foams were prepared employing above-described BlendedSurfactants Q and R of this invention (and above described ControlSurfactants AA and CC, not of this invention) as the foam stabilizingcomponents of Foam Formulations C and D which contained 5.0 and 3.6parts water per 100 parts of polyester polyol, respectively. The purposeof these examples was to determine whether the acrylonitrile-cappedpolyoxyalkylene-polysiloxane polymers of the invention as illustrated bySurfactant P contained in Blended Surfactants Q and R are capable ofproviding semicommercial size foam buns having acceptable physicalproperties. In these examples, a Hennecke UBT-63 high pressurecontinuous polyurethane foam machine was used to which the followingthree streams was added (1) the polyester polyol; (2) the activatorstream containing water, amine catalysts and foam-stabilizingsurfactants; and (3) the polyisocyanate reactant. The mixer speed wasabout 5000 revolutions per minute and the head pressure was 12-17 poundsper square inch. At ambient temperature the emerging foam mixture waspoured onto paper on a continuously moving conveyor belt. The foams wereallowed to set and cure in the form of large slabs (12 feet in length,22 inches wide and 18 inches high). After 24 hours of aging at ambienttemperatures the foams were cut and submitted for physical propertymeasurements. In using Blended Surfactants Q and R, clear homogeneousaqueous premixtures were obtained when the water and amine catalysts ofthe foam formulations were combined therewith. The composition of FoamFormulations C and D, the amount of the blended surfactants employed ineach example, and the results are given in Table X and XI which follow.

                                      TABLE X                                     __________________________________________________________________________    POLYESTER POLYOL-BASED FOAMS (Machine Runs)                                   EXAMPLE No.         58   59   60   61   62   63   64                          __________________________________________________________________________    Foam Formulation C, Parts by Weight                                           Polyester Polyol /1/                                                                              100  100  100  100  100  100  100                         Polyisocyanate /1/ (Index = 105)                                                                  59.2 59.2 59.2 59.2 59.2 59.2 59.2                        Water               5.0  5.0  5.0  5.0  5.0  5.0  5.0                         Total Blended Surfactant                                                                          1.0  1.0  0.5  1.0  0.5  0.5  0.5                          Control AA/2/      1.0  --   --   --   --   --   --                           Control CC /2/     --   1.0  0.5  --   --   --   --                           Q/3/               --   --   --   0.50 0.25 0.375                                                                              0.125                        R/3/               --   --   --   0.50 0.25 0.125                                                                              0.375                       N-ethylmorpholine   2.0  2.0  2.0  2.0  2.0  2.0  2.0                         Hexadecyldimethylamine                                                                            0.3  0.3  0.3  0.3  0.3  0.3  0.3                         Cream Time, seconds 3    3    3    --   3    3    3                           Rise Time, seconds  46   47   45   --   44   46   47                          Gel Time, seconds   80   81   81   --   83   82   --                          Foam Properties                                                               Foam Density, lbs./ft..sup.3                                                                      1.21 1.23 S    1.25 1.25 1.21 1.25                        Breathability, SCFM 0.214                                                                              0.240     0.389                                                                              0.263                                                                              0.915                                                                              0.974                       ILD (4"), lbs./50 in..sup.2   P                                                25%                50.7 56.9      51.0 48.2 50.1 48.3                         65%                96.0 125  L    27.4 25.0 24.9 26.2                        Compression Sets, %                                                            50%                16.7 16.8 I    --   14.6 12.6 14.7                         75%                26.5 50.0      --   23.7 13.2 15.1                         90%                65.4 74.4 T    15.5 61.6 18.6 25.7                        Tensile strength, p.s.i.                                                                          26.9 24.8      21.2 19.1 22.1 20.8                        Elongation, %       236  256  S    205  186  255  219                         Tear Resistance, lbs./in.                                                                         3.19 3.86      4.3  4.0  3.7  3.5                         CPI                 40-45                                                                              40-45     40-45                                                                              40-45                                                                              40-45                                                                              40-45                       __________________________________________________________________________     /1/ As defined in Table I                                                     /2/ AA and CC Surfactants not of this invention                               /3/ As defined in Table IX                                               

                                      TABLE XI                                    __________________________________________________________________________    POLYESTER POLYOL-BASED FOAMS (Machine Runs)                                   EXAMPLE No.           65   66   67                                            __________________________________________________________________________    Foam Formulation D, Parts by Weight                                           Polyester Polyol /1/  100  100  100                                           Polyisocyanate /1/ (Index = 105)                                                                    45.2 45.2 45.2                                          Water                 3.6  3.6  3.6                                           Total Blended Surfactant                                                                            1.0  2.0  1.0                                            Control CC/2/        1.0  --   --                                             Q/3/                 --   1.0  0.5                                            R/3/                 --   1.0  0.5                                           3-Dimethylaminopropionitrile/Bis[2-(N,N-                                                            2.0  2.0  2.0                                           dimethylamino)ethyl]ether (95/5)                                              Hexadecyldimethylamine                                                                              0.3  0.3  0.3                                           Cream Time, seconds   2.5  2.5  2.5                                           Rise Time, seconds    56   56   --                                            Gel Time, seconds     81   78   --                                            Foam Properties                                                               Foam density, lbs./ft..sup.3                                                                        1.61 1.65 1.70                                          Breathability, SCFM   0.678                                                                              2.54 1.44                                          ILD (4"), lbs./50 in..sup.2                                                    25%                  52.2 43.7 47.7                                           65%                  84.5 70.2 79.0                                           25% return           28.9 24.8 28.0                                          Compression Set, 90%  8.5  8.4  10.8                                          Tensile strength, p.s.i.                                                                            22.2 23.6 24.8                                          Elongation, %         308  331  316                                           Tear Resistance, lbs./in.                                                                           3.5  3.9  3.7                                           CPI                   50-55                                                                              50-55                                                                              50-55                                         __________________________________________________________________________     /1/ As defined in Table I                                                     /2/ AA and CC-Surfactants not of this invention                               /3/ As defined in Table IX                                               

The data of Tables X and XI above demonstrate that theacrylonitrile-capped polyoxyalkylene-polysiloxane polymers of thisinvention possess a highly desirable combination of properties such asthe ability to form clear homogeneous premixes, potency and the abilityto provide over a wide processing latitude flexible polyesterpolyurethane foam having good physical properties.

Various modifications and variations of this invention will be obviousto a worker skilled in the art and it is to be understood that suchmodifications and variations are to be included within the purview ofthis application and the spirit and scope of the appended claims.

What is claimed is:
 1. An acrylonitrile-cappedpolyoxyalkylene-polysiloxane polymer containing at least onesilicon-bonded acrylonitrile-capped polyoxyalkylene radical having theaverage formula --R"(X)_(q) (OC₃ H₆)_(n) (OC₂ H₄)_(m) OCH₂ CH₂ CNwherein R" is an alkylene radical, free from unsaturation, andcontaining from 2 to 6 carbon atoms, wherein X is a bridging groupselected from the class consisting of --CO-- and --NHCO--, wherein q hasa value of 0 or 1, wherein m has a value of from 4 to 30 and wherein nhas a value of from 0 to
 10. 2. A polymer as defined in claim 1, whereinR" is --CH₂ CH₂ CH₂ --, q is 0, m has a value of 4 to 15 and n is
 0. 3.An acrylonitrile-capped polyoxyalkylene-polysiloxane polymer as definedin claim 1 having the average composition formula ##STR43## wherein R isa monovalent hydrocarbon radical, wherein Q is an acrylonitrile-cappedpolyoxyalkylene radical having the average formula

    --R"(X).sub.q (OC.sub.3 H.sub.6).sub.n (OC.sub.2 H.sub.4).sub.m OCH.sub.2 CH.sub.2 CN

wherein E.sup.. is a radical selected from the class consisting of acyano-containing group of the formula --(O)_(r) R² CN wherein r has avalue of 0 or 1 and R² is an alkylene radical having from 2 to 12 carbonatoms, a cyano-containing group of the formula --(O)_(r) R² OR² CNwherein r and R² are the same as defined above, asulfolanyloxyalkyl-containing group of the formula ##STR44## wherein R³is an alkylene radical having from 2 to 8 carbon atoms and R⁴, R⁵, R⁶and R⁷ are independently hydrogen or alkyl radicals having from 1 to 4carbon atoms, and a morpholino-containing group of the formula ##STR45##wherein t has a value from 0 to 4, s is 0 or 1 provided s is 1 when thas a value of more than 1, wherein R⁸ is an alkylene radical havingfrom 2 to 4 carbon atoms, wherein R⁹ is an alkylene radical having from2 to 6 carbon atoms, and wherein R⁴, R⁵, R⁶ and R⁷ are the same asdefined above; wherein a, b, and c are 0 or any positive number havingan average value of no more than 2 and the average value of the sum ofa+b+c is 2, wherein d is 0 or any positive number having an averagevalue of up to about 20, wherein e is 0 or any positive number having anaverage value of up to about 30, and wherein f is 0 or any positivenumber having an average value of up to about 20, provided the averagevalue of the sum of b+e is at least about 0.5 up to about
 30. 4. Anacrylonitrile-capped polyoxyalkylene-polysiloxane polymer as defined inclaim 1 having the average composition formula ##STR46## wherein R is amonovalent hydrocarbon radical, wherein Q is an acrylonitrile-cappedpolyoxyalkylene radical having the average formula

    --R"(X).sub.q (OC.sub.3 H.sub.6).sub.n (OC.sub.2 H.sub.4).sub.m OCH.sub.2 CH.sub.2 CN

and wherein the mole ratio of the SiO4/2 units to total polyfunctionalunits to total monofunctional units is defined by g:h:i in which theratio of g:h is from about 0.4:1 to about 2:1 and the ratio of i:h isfrom about 0.2:1 to about 2:1.
 5. An acrylonitrile-cappedpolyoxyalkylene-polysiloxane polymer as defined in claim 1 having theaverage composition formula ##STR47## wherein R is a monovalenthydrocarbon radical wherein Q is an acrylonitrile-capped polyoxyalkyleneradical having the average formula

    --R"(X).sub.q (OC.sub.3 H.sub.6).sub.n (OC.sub.2 H.sub.4).sub.m OCH.sub.2 CH.sub.2 CN

and wherein the mole ratio of the SiO4/2 units to total Q substitutedsiloxy units to total trihydrocarbylsiloxy units is defined by j:k:p inwhich the ratio of j:k is from about 0.75:1 to about 2:1, and the ratioof p:k is from about 0.1:1 to about 1:1.
 6. A polymer as defined inclaim 3 wherein R is methyl, R" is --CH₂ CH₂ CH₂ --, q, is 0, m has avalue of 4 to 15, n is 0, a is 0, and b is 0 and c is
 0. 7. A polymer asdefined in claim 3 having the average composition formula ##STR48##wherein E is a cyano-containing group having the formula --(O)_(r) R²CN, wherein x has an average value of 0.5 to 20, y has an average valueof 0.5 to 30 and z has an average value of 0.5 to
 20. 8. A polymer asdefined in claim 7 wherein x has an average value of 1 to 10, wherein yhas an average value of 1 to 10, wherein z has an average value of 1 to10, wherein r is 0, wherein R is methyl and wherein R² is an alkyleneradical having from 2 to 4 carbon atoms.
 9. A polymer as defined inclaim 8 wherein R" and R² are --CH₂ CH₂ CH₂ -- wherein q is 0, m has avalue of 4 to 15, and n is
 0. 10. A polymer as defined in claim 7 havingthe average composition formula ##STR49## wherein Me is a methylradical.
 11. A polymer as defined in claim 7 having the averagecomposition formula ##STR50## wherein Me is a methyl radical.
 12. Apolymer as defined in claim 7 having the average composition formula##STR51##
 13. A polymer as defined in claim 3 having the averagecomposition formula ##STR52## wherein x has an average value of 0.5 to20 and y has an average value of 0.5 to
 30. 14. A polymer as defined inclaim 13 wherein x has an average value of 1 to 10 wherein y has anaverage value of 1 to 10 and wherein R is a methyl radical.
 15. Apolymer as defined in claim 14 wherein R" is --CH₂ CH₂ CH₂ --, wherein qis 0, m has a value of 4 to 15 and n is
 0. 16. A polymer as defined inclaim 13 having the average composition formula ##STR53## wherein Me isa methyl radical.
 17. A polymer as defined in claim 13 having theaverage composition formula ##STR54## wherein Me is a methyl radical.18. A polymer as defined in claim 13 having the average compositionformula ##STR55## wherein Me is a methyl radical.
 19. A polymer asdefined in claim 13 having the average composition formula ##STR56##wherein Me is a methyl radical.
 20. A polymer as defined in claim 13having the average composition formula ##STR57##
 21. A polymer asdefined in claim 13 having the average composition formula ##STR58##wherein Me is a methyl radical.
 22. A polymer as defined in claim 13having the average formula ##STR59##
 23. A process for producingpolyurethane foam which comprises eimultaneously reacting and foaming areaction mixture comprising (a) an organic polyol reactant containing anaverage of at least two hydroxyl groups per molecule; (b) an organicpolyisocyanate reactant containing at least two isocyanato groups permolecule; (c) a blowing agent; (d) an amine catalyst and (e) a foamstabilizer comprising an acrylonitrile-cappedpolyoxyalkylene-polysiloxane polymer as defined in claim
 1. 24. Aprocess as defined in claim 23, in which said reaction mixture containsan organic flame-retardant as an additional component thereof.
 25. Aprocess for producing flexible polyester polyurethane foam whichcomprises simultaneously reacting and foaming a reaction mixturecomprising (a) a polyester polyol reactant containing an average of atleast two hydroxyl groups per molecule; (b) an organic polyisocyanatereactant containing at least two isocyanato groups per molecule; (c)water as a source of blowing action; (d) a tertiary amine catalyst; and(f) a foam stabilizer comprising an acrylonitrile-cappedpolyoxyalkylene-polysiloxane polymer as defined in claim
 7. 26. Aprocess as defined in claim 25 in which said reaction mixture containsan organic flame-retardant as an additional component thereof.
 27. Aprocess for producing flexible polyester polyurethane foam whichcomprises simultaneously reacting and foaming a reaction mixturecomprising (a) a polyester polyol reactant containing an average of atleast two hydroxyl groups per molecule; (b) an organic polyisocyanatereactant containing at least two isocyanato groups per molecule; (c)water as a source of blowing action; (d) a tertiary amine catalyst; and(f) a foam stabilizer comprising an acrylonitrile-cappedpolyoxyalkylene-polysiloxane polymer as defined in claim
 13. 28. Aprocess as defined in claim 27 in which said reaction mixture containsan organic flame-retardant as an additional component thereof.
 29. Aprocess for producing flexible polyester polyurethane foam whichcomprises simultaneously reacting and foaming a reaction mixturecomprising (a) a polyester polyol reactant containing an average of atleast two hydroxyl groups per molecule; and (b) an organicpolyisocyanate reactant containing at least two isocyanato groups permolecule; (c) water as a source of blowing action; (d) a tertiary aminecatalyst; and (f) a foam stabilizer comprising an acrylonitrile-cappedpolyoxyalkylene-polysiloxane polymer as defined in claim
 14. 30. Aprocess as defined in claim 29 in which said reaction mixture containsan organic flame-retardant as an additional component thereof.
 31. Aprocess for producing flexible polyester polyurethane foam whichcomprises simultaneously reacting and foaming a reaction mixturecomprising (a) a polyester polyol reactant containing an average of atleast two hydroxyl groups per molecule: (b) an organic polyisocyanatereactant containing at least two isocyanato groups per molecule; (c)water as a source of blowing action; (d) a tertiary amine catalyst; and(f) a foam stabilizer comprising an acrylonitrile-cappedpolyoxyalkylene-polysiloxane polymer as defined in claim
 15. 32. Aprocess as defined in claim 31 in which said reaction mixture containsan organic flame-retardant as an additional component thereof.
 33. Apolyurethane foam as produced by the process of claim
 24. 34. Apolyurethane foam as produced by the process of claim
 26. 35. Apolyurethane foam as produced by the process of claim
 28. 36. Apolyurethane foam as produced by the process of claim
 30. 37. Apolyurethane foam as produced by the process of claim 32.